Bifunctional phenyl iso(thio)cyanates, processes and intermediates products for their preparation

ABSTRACT

A process for preparing phenyl iso(thio)cyanates of the formula I in which a compound of the formula II or its HCl adduct is reacted with a phosgenating agent 
                         
where W is oxygen or sulfur and Ar and A are as defined in claim  1  is described.
 
     Moreover, the invention relates to the use of the phenyl iso(thio)cyanates for preparing crop protection agents.

This application is a divisional of U.S. Ser. No. 12/886,986, filed Sep. 21, 2010, which is a divisional of U.S. Ser. No. 10/532,931, filed Apr. 28, 2005, now U.S. Pat. No. 7,820,846 issued Oct. 26, 2010, which is a 35 USC §371 National Phase Entry Application from PCT/EP03/012013, filed Oct. 29, 2003, and designating the United States, which claims the benefit of German Patent Application No. 102 50 614.0 filed Oct. 30, 2002 the disclosures of which are incorporated herein in their entirety by reference.

The invention relates to a process for preparing bifunctional phenyl iso(thio)cyanates of the formula I having an acylsulfonamide group

where the Variables are as defined below:

-   W is oxygen or sulfur, -   Ar is phenyl which may be mono- or polysubstituted by the following     groups: hydrogen, halogen, C₁-C₄-haloalkyl or cyano, -   A is a radical derived from a primary or secondary amine or is NH₂,     by reacting anilines or their hydrochlorides with phosgene     derivatives. The invention also relates to bifunctional phenyl     iso(thio)cyanates.

Iso(thio)cyanatobenzoylsulfamic acid amides are potential precursors for the preparation of crop protection agents having a triazole-3,5-dion-4-yl group, pyrimidine-2,6-dion-1-yl group or 1,3,5-triazine-2,4,6-trion-1-yl group or their S analogs as described, for example, in WO 01/83459. Owing to their reactivity, it should be easy to convert the iso(thio)cyanato structural unit into other groups such as (thio)urea or urethane groups. However, for the reasons mentioned below, their preparation was thought to be impossible.

In principle, phenyl iso(thio)cyanates can be prepared by reacting primary aromatic amines with phosgene and thiophosgene, respectively (see, for example, Houben-Weyl, Methoden der organischen Chemie [methods of organic chemistry], 4th edition, Vol. IX, pp. 869, 875-877 and Vol. VIII, pp. 120-124). Further general processes are known, for example, from EP 70389, EP 75267 and EP 409 025.

Common to all of the processes described is that the phenyl iso(thio)cyanates used do not carry an acylsulfonamide group. This is because it is known that an iso(thio)cyanato group can react with a sulfonamide group with formation of sulfonylureas. Thus, for example, J. Cervello and T. Sastre describe, in Synthesis 1990, 221-222, the reaction of a sulfonamide with isocyanates according to the equation below:

U.S. Pat. No. 4,309,209 discloses that phenyl isocyanates react with chloromethane-(N-methyl)sulfonamide(═ClCH₂SO₂NHCH₃) with formation of a 1,2,4-thiadiazolidine-1,1,3-trione. P. Schwenkkraus and H.-H. Otto describe, in Arch. Pharm. (Weinheim), 326 (1993), 437-441, the reaction of 3-haloalkyl-β-sultames with phenyl isocyanate with formation of carbamoyl compounds.

DE 3433391 discloses the reaction of saccharin with acyl isocyanates to give N-acylated saccharin derivatives.

In JZV Akad Nauk SSSR, Ser Khim 1990, 2874 (English translation: Bulletin of the Academy of Sciences of the USSR, Division of Chemical Sciences, Vol. 39, (1990), p. 2610), B. A. Arbuzov, N. N. Zobova and N. R. Fedotava describe the N- and O-acylation of saccharin by reaction with a trifluoroacetyl isocyanate.

Against this background, both the preparation of phenyl iso(thio)cyanates which, in the same molecule, also carry a reactive acylsulfonamide function and their isolation—without subsequent intermolecular reactions—have been thought to be impossible. A person skilled in the art would have assumed that, owing to their acidic proton, sulfonamides would react with phenyl iso(thio)cyanates to give sulfonylurea derivatives. Hitherto, no process for the preparation of phenyl iso(thio)cyanates which, as further functional group, carry an acylsulfonamide group has been described.

It is an object of the present invention to provide iso(thio)cyanatobenzoylsulfamic acid amides of the formula I.

We have found that this object is achieved, surprisingly, by a process in which an aminobenzoylsulfamic acid amide of the formula II

where the variables Ar and A are as defined above is reacted with phosgene, diphosgene or thiophosgene.

Accordingly, the present invention relates to a process for preparing phenyl iso(thio)cyanates of the formula I which comprises reacting a compound of the formula II or its HCl adduct with phosgene, thiophosgene or diphosgene (see Scheme 1). In Scheme 1, the variables Ar, A and W are as defined above.

The phenyl iso(thio)cyanates I obtainable in high yield by the process according to the invention are useful intermediates for the preparation of crop protection agents, in particular of 3-(thiazolidinone)-substituted phenylsulfamoylcarboxamides. Accordingly, the present invention also provides a process for preparing 3-heterocyclyl-substituted phenylsulfamoylcarboxamides starting with phenyl iso(thio)cyanates I. Contrary to expectation, the compounds I according to the invention are stable compounds which are readily prepared, even on an industrial scale. Accordingly, the invention also relates to the phenyl iso(thio)cyanates of the formula I. The stability of the compounds I according to the invention is surprising, since a person skilled in the art would have expected an intermolecular reaction between the iso(thio)cyanato structural unit and the sulfamide grouping to take place.

The organic molecular moieties mentioned in the definition of the substituents are—like the term halogen—collective terms for individual enumerations of the individual group members, where the term C_(n)-C_(m) indicates the possible number of carbon atoms in the molecular moiety. All carbon chains, i.e. all alkyl, alkenyl and alkynyl moieties, may be straight-chain or branched. Unless indicated otherwise, halogenated substituents preferably carry one to six identical or different halogen atoms. In each case, the term “halogen” denotes fluorine, chlorine, bromine or iodine.

Examples of other meanings are:

-   -   C₁-C₄-alkyl: for example methyl, ethyl, propyl, 1-methylethyl,         butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl;     -   C₁-C₁₀-alkyl: a saturated aliphatic hydrocarbon radical having 1         to 10 carbon atoms, for example C₁-C₄-alkyl as mentioned above,         and also, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl,         3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,         1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,         2-methylpentyl, 3-methylpentyl, 4-methylpentyl,         1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl,         2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl,         1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,         1-ethyl-1-methylpropyl, 1-ethyl-3-methylpropyl, n-heptyl,         n-nonyl, n-decyl, 1-methylhexyl, 1-ethylhexyl, 1-methylheptyl,         1-methyloctyl, 1-methylnonyl;     -   C₂-C₁₀-alkenyl: a monounsaturated olefinic hydrocarbon radical         having 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, for         example ethenyl, prop-2-en-1-yl (=allyl), prop-1-en-1-yl,         but-1-en-4-yl, but-2-en-1-yl, but-3-en-1-yl,         1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, 1-penten-3-yl,         1-penten-4-yl, 2-penten-4-yl, 1-methylbut-2-en-1-yl,         2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl,         1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl,         3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl,         1,2-dimethylprop-2-en-1-yl, 1-ethylprop-2-en-1-yl,         1-ethylprop-1-en-2-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl,         hex-3-en-1-yl, hex-4-en-1-yl, hex-5-en-1-yl,         1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl,         3-methylpent-1-en-1-yl, 4-methylpent-1-en-1-yl,         1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl,         3-methylpent-2-en-1-yl, 4-methylpent-2-en-1-yl,         1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl,         3-methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl,         1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl,         3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl,         1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl,         1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl,         1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl,         2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-2-en-1-yl,         2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-2-en-1-yl,         1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl,         2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl,         1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl,         1-ethyl-2-methylprop-2-en-1-yl, hept-2-en-1-yl, oct-2-en-1-yl,         non-2-en-1-yl, dec-2-en-1-yl;     -   C₂-C₁₀-alkynyl: a hydrocarbon radical having 2 to 10 carbon         atoms, preferably 3 to 6 carbon atoms, and one triple bond, for         example ethynyl, prop-2-yn-1-yl (=propargyl), prop-1-yn-1-yl,         but-1-yn-1-yl, but-1-yn-3-yl, but-1-yn-4-yl, but-2-yn-1-yl,         pent-1-yn-1-yl, pent-1-yn-3-yl, pent-1-yn-4-yl, pent-1-yn-5-yl,         pent-2-yn-1-yl, pent-2-yn-4-yl, pent-2-yn-5-yl,         3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, hex-1-yn-3-yl,         hex-1-yn-4-yl, hex-1-yn-5-yl, hex-1-yn-6-yl, hex-2-yn-1-yl,         hex-2-yn-4-yl, hex-2-yn-5-yl, hex-2-yn-6-yl, hex-3-yn-1-yl,         hex-3-yn-2-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl,         3-methylpent-1-yn-5-yl, 4-methylpent-2-yn-4-yl,         4-methylpent-2-yn-5-yl, hept-2-yn-1-yl, Oct-2-yn-1-yl,         non-2-yn-1-yl, dec-2-yn-1-yl;     -   C₁-C₄-haloalkyl: a C₁-C₄-alkyl radical as mentioned above which         is partially or fully substituted by fluorine, chlorine, bromine         and/or iodine, i.e., for example, chloromethyl, dichloromethyl,         trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,         chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,         2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl,         2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl,         2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl,         2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl,         3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl,         2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl,         2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl,         3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl,         heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl,         1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl,         4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;     -   C₁-C₁₀-haloalkyl: C₁-C₁₀-alkyl as mentioned above in which 1 to         6 hydrogen atoms are substituted by halogen atoms, preferably by         fluorine and/or chlorine, for example: C₁-C₄-haloalkyl as         mentioned above, and also 5-fluoropentyl, 5-chloropentyl,         5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl,         6-chlorohexyl, 6-bromohexyl or 6-iodohexyl;     -   C₂-C₁₀-haloalkenyl: C₂-C₁₀-alkenyl as mentioned above in which 1         to 6 hydrogen atoms are substituted by halogen atoms, preferably         by fluorine and/or chlorine: for example 2-chloroallyl,         3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl,         2,3,3-trichloroallyl, 2,3-dichlorobut-2-en-1-yl, 2-bromoallyl,         3-bromoallyl, 2,3-dibromoallyl, 3,3-dibromoallyl,         2,3,3-tribromoallyl or 2,3-dibromobut-2-en-1-yl;     -   C₂-C₁₀-haloalkynyl: C₂-C₁₀-alkynyl as mentioned above in which 1         to 6 hydrogen atoms are substituted by halogen atoms, preferably         by fluorine and/or chlorine: for example         1,1-difluoroprop-2-yn-1-yl, 1,1-difluorobut-2-yn-1-yl,         4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl,         5-fluoropent-3-yn-1-yl or 6-fluorohex-4-yn-1-yl;     -   C₁-C₁₀-cyanoalkyl: C₁-C₁₀-alkyl substituted by a CN group, for         example cyanomethyl, 1-cyanoethyl, 2-cyanoethyl, 1-cyanopropyl,         2-cyanopropyl, 3-cyanopropyl, 1-cyanoprop-2-yl,         2-cyanoprop-2-yl, 1-cyanobutyl, 2-cyanobutyl, 3-cyanobutyl,         4-cyanobutyl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 1-cyanobut-3-yl,         2-cyanobut-3-yl, 1-cyano-2-methylprop-3-yl,         2-cyano-2-methylprop-3-yl, 3-cyano-2-methylprop-3-yl,         3-cyano-2,2-dimethylpropyl, 6-cyanohex-1-yl, 7-cyanohept-1-yl,         8-cyanooct-1-yl, 9-cyanonon-1-yl, 10-cyanodec-1-yl;     -   C₃-C₁₀-cycloalkyl: a cycloaliphatic radical having 3 to 10         carbon atoms: for example cyclopropyl, cyclobutyl, cyclopentyl,         -   cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or             cyclodecyl;     -   C₃-C₁₀-cycloalkenyl: a cycloaliphatic radical having 3 to 10         carbon atoms and a double bond: for example cyclopropen-1-yl,         cyclobuten-1-yl, cyclopenten-1-yl, cyclohexen-1-yl,         cyclohepten-1-yl, cycloocten-1-yl, cyclononen-1-yl,         cyclodecen-1-yl, cyclopent-2-en-1-yl, cyclohex-2-en-1-yl,         cyclohept-2-en-1-yl, cyclooct-2-en-1-yl, cyclonon-2-en-1-yl,         cyclodec-2-en-1-yl, cyclohex-3-en-1-yl, cyclohept-3-en-1-yl,         cyclooct-3-en-1-yl, cyclooct-4-en-1-yl, cyclonon-3-en-1-yl,         cyclonon-4-en-1-yl, cyclodec-4-en-1-yl or cyclodec-3-en-1-yl;     -   C₁-C₄-alkylcarbonyl: an alkyl radical having 1 to 4 carbon atoms         which is attached via a carbonyl group, for example acetyl,         propionyl, butyryl or isobutyryl;     -   (C₁-C₄-alkylamino)carbonyl: for example methylaminocarbonyl,         ethylaminocarbonyl, propylaminocarbonyl,         1-methylethylaminocarbonyl, butylaminocarbonyl,         1-methylpropylaminocarbonyl, 2-methylpropylaminocarbonyl or         1,1-dimethylethylaminocarbonyl;     -   di-(C₁-C₄-alkyl)aminocarbonyl: for example         N,N-dimethylaminocarbonyl, N,N-diethylaminocarbonyl,         N,N-di-(1-methylethyl)aminocarbonyl, N,N-dipropylaminocarbonyl,         N,N-dibutylaminocarbonyl, N,N-di-(1-methylpropyl)aminocarbonyl,         N,N-di-(2-methylpropyl)aminocarbonyl,         N,N-di-(1,1-dimethylethyl)aminocarbonyl,         N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl,         N-methyl-N-(1-methylethyl)aminocarbonyl,         N-butyl-N-methylaminocarbonyl,         N-methyl-N-(1-methylpropyl)aminocarbonyl,         N-methyl-N-(2-methylpropyl)aminocarbonyl,         N-(1,1-dimethylethyl)-N-methylaminocarbonyl,         N-ethyl-N-propylaminocarbonyl,         N-ethyl-N-(1-methylethyl)aminocarbonyl,         N-butyl-N-ethylaminocarbonyl,         N-ethyl-N-(1-methylpropyl)aminocarbonyl,         N-ethyl-N-(2-methylpropyl)aminocarbonyl,         N-ethyl-N-(1,1-dimethylethyl)aminocarbonyl,         N-(1-methylethyl)-N-propylaminocarbonyl,         N-butyl-N-propylaminocarbonyl,         N-(1-methylpropyl)-N-propylaminocarbonyl,         N-(2-methylpropyl)-N-propylaminocarbonyl,         N-(1,1-dimethylethyl)-N-propylaminocarbonyl,         N-butyl-N-(1-methylethyl)aminocarbonyl,         N-(1-methylethyl)-N-(1-methylpropyl)aminocarbonyl,         N-(1-methylethyl)-N-(2-methylpropyl)aminocarbonyl,         N-(1,1-dimethylethyl)-N-(1-methylethyl)aminocarbonyl,         N-butyl-N-(1-methylpropyl)aminocarbonyl,         N-butyl-N-(2-methylpropyl)aminocarbonyl,         N-butyl-N-(1,1-dimethylethyl)aminocarbonyl,         N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl,         N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminocarbonyl or         N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminocarbonyl;     -   C₁-C₄-alkoxy: an alkyl radical having 1 to 4 carbon atoms which         is attached via an oxygen atom, for example methoxy, ethoxy,         propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy,         2-methylpropoxy or 1,1-dimethylethoxy;     -   C₁-C₄-alkoxycarbonyl: an alkoxy radical having 1 to 4 carbon         atoms which is attached via a carbonyl group, for example         methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,         1-methylethoxycarbonyl, butoxycarbonyl, 1-methylpropoxycarbonyl,         2-methylpropoxycarbonyl or 1,1-dimethylethoxycarbonyl;     -   C₁-C₄-alkylthio(C₁-C₄-alkylsulfanyl: C₁-C₄-alkyl-S—): an alkyl         radical having 1 to 4 carbon atoms which is attached via a         sulfur atom, for example methylthio, ethylthio, propylthio,         1-methylethylthio, butylthio, 1-methylpropylthio,         2-methylpropylthio or 1,1-dimethylethylthio;     -   C₁-C₄-alkylsulfinyl(C₁-C₄-alkyl-S(═O)—): for example         methylsulfinyl, ethylsulfinyl, propylsulfinyl,         1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl,         2-methylpropylsulfinyl or 1,1-dimethylethylsulfinyl;     -   C₁-C₄-alkylsulfonyl(C₁-C₄-alkyl-S(═O)₂—): for example         methylsulfonyl, ethylsulfonyl, propylsulfonyl,         1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl,         2-methylpropylsulfonyl or 1,1-dimethylethylsulfonyl;     -   3- to 8-membered heterocyclyl: a heterocyclic radical which has         3, 4, 5, 6, 7 or 8 ring members, 1, 2 or 3 of the ring members         being heteroatoms selected from the group consisting of oxygen,         sulfur, nitrogen and a group NR⁶ (where R⁶ is hydrogen,         C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl). Moreover, the         heterocycle may optionally have one or two carbonyl groups or         thiocarbonyl groups as ring members. The heterocycle may be         aromatic (heteroaryl) or partially or fully saturated.     -   Examples of saturated heterocycles are:     -   oxiran-1-yl, aziridin-1-yl, oxetan-2-yl, oxetan-3-yl,         thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl,         azetidin-3-yl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl,         tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl,         pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl,         1,3-dioxolan-2-yl, 1,3-dioxolan-4-yl, 1,3-oxathiolan-2-yl,         1,3-oxathiolan-4-yl, 1,3-oxathiolan-5-yl, 1,3-oxazolidin-2-yl,         1,3-oxazolidin-3-yl, 1,3-oxazolidin-4-yl, 1,3-oxazolidin-5-yl,         1,2-oxazolidin-2-yl, 1,2-oxazolidin-3-yl, 1,2-oxazolidin-4-yl,         1,2-oxazolidin-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl,         pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl,         tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl,         tetrahydropyrazol-4-yl, tetrahydropyran-2-yl,         tetrahydropyran-3-yl, tetrahydropyran-4-yl,         tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl,         tetrahydropyran-4-yl, piperidin-1-yl, piperidin-2-yl,         piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl,         1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl,         1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl,         1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl,         morpholin-2-yl, morpholin-3-yl, morpholin-4-yl,         hexahydropyridazin-1-yl, hexahydropyridazin-3-yl,         hexahydropyridazin-4-yl, hexahydropyrimidin-1-yl,         hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl,         hexahydropyrimidin-5-yl, piperazin-1-yl, piperazin-2-yl,         piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl,         hexahydro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl,         oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan-4-yl,         1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl,         1,3-dioxepan-6-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-4-yl,         1,3-dithiepan-5-yl, 1,3-dithiepan-2-yl, 1,4-dioxepan-2-yl,         1,4-dioxepan-7-yl, hexahydroazepin-1-yl, hexahydroazepin-2-yl,         hexahydroazepin-3-yl, hexahydroazepin-4-yl,         hexahydro-1,3-diazepin-1-yl, hexahydro-1,3-diazepin-2-yl,         hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diazepin-1-yl and         hexahydro-1,4-diazepin-2-yl;     -   examples of unsaturated heterocycles are:     -   dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl,         1,3-oxazolin-2-yl;     -   examples of aromatic heterocyclyl are the 5- and 6-membered         aromatic heterocyclic radicals, for example furyl, such as         2-furyl and 3-furyl, thienyl, such as 2-thienyl and 3-thienyl,         pyrrolyl, such as 2-pyrrolyl and 3-pyrrolyl, isoxazolyl, such as         3-isoxazolyl, 4-isoxazolyl and 5-isoxazolyl, isothiazolyl, such         as 3-isothiazolyl, 4-isothiazolyl and 5-isothiazolyl, pyrazolyl,         such as 3-pyrazolyl, 4-pyrazolyl and 5-pyrazolyl, oxazolyl, such         as 2-oxazolyl, 4-oxazolyl and 5-oxazolyl, thiazolyl, such as         2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl, such as         2-imidazolyl and 4-imidazolyl, oxadiazolyl, such as         1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl and         1,3,4-oxadiazol-2-yl, thiadiazolyl, such as         1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and         1,3,4-thiadiazol-2-yl, triazolyl, such as 1,2,4-triazol-1-yl,         1,2,4-triazol-3-yl and 1,2,4-triazol-4-yl, pyridinyl, such as         2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl, such as         3-pyridazinyl and 4-pyridazinyl, pyrimidinyl, such as         2-pyrimidinyl, 4-pyrimidinyl and 5-pyrimidinyl, furthermore         2-pyrazinyl, 1,3,5-triazin-2-yl and 1,2,4-triazin-3-yl, in         particular pyridyl, furanyl and thienyl.

The radical A, which is derived from a primary or secondary amine, is generally a group of the formula —NR¹R²,

where the variables R¹ and R² are as defined below:

-   R¹ and R² independently of one another represent hydrogen,     C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl or C₂-C₁₀-alkynyl which may be     unsubstituted or substituted by one of the following radicals:     C₁-C₄-alkoxy, C₁-C₄-alkylthio, CN, NO₂, formyl, C₁-C₄-alkylcarbonyl,     C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylaminocarbonyl,     C₁-C₄-dialkylaminocarbonyl, C₁-C₄-alkylsulfinyl,     C₁-C₄-alkylsulfonyl, C₃-C₁₀-cycloalkyl, 3-to 8-membered heterocyclyl     having one, two or three heteroatoms selected from the group     consisting of O, S, N and a group NR⁶ (where R⁶ is hydrogen,     C₁-C₈-alkyl, C₃-C₆-alkenyl or C₃-C₈-alkynyl), phenyl, which for its     part may have 1, 2, 3 or 4 substituents selected from the group     consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-fluoroalkyl,     C₁-C₄-alkyloxycarbonyl, trifluoromethylsulfonyl, C₁-C₃-alkylamino,     C₁-C₃-dialkylamino, formyl, nitro and cyano,     -   C₁-C₁₀-haloalkyl, C₂-C₁₀-haloalkenyl, C₂-C₁₀-haloalkynyl,         C₃-C₈-cycloalkyl, C₃-C₁₀-cycloalkenyl, 3- to 8-membered         heterocyclyl having one to three heteroatoms selected from the         group consisting of O, S, N and a group NR⁶ (where R⁶ is         hydrogen, C₁-C₈-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl), phenyl         or naphthyl, where C₃-C₈-cycloalkyl, C₃-C₁₀-cycloalkenyl, 3-to         8-membered heterocyclyl, phenyl and naphthyl may for their part         have 1, 2, 3 or 4 substituents selected from the group         consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy,         C₁-C₄-fluoroalkyl, C₁-C₄-alkyloxycarbonyl,         trifluoromethylsulfonyl, formyl, C₁-C₃-alkylamino,         C₁-C₃-dialkylamino, phenoxy, nitro and cyano, or -   R¹ and R² together form a saturated or partially unsaturated 5- to     8-membered nitrogen heterocycle which for its part may be     substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy and/or C₁-C₄-haloalkyl and     may have one or two carbonyl groups, thiocarbonyl groups and/or one     or two further heteroatoms selected from the group consisting of O,     S, N and a group NR⁶ (where R⁶ is as defined above) as ring members.

Preferred substituents R¹ and R² are, independently of one another, selected from the group consisting of hydrogen, C₁-C₆-alkyl, which is unsubstituted or substituted by a substituent selected from the group consisting of halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₃-C₈-cycloalkyl, phenyl, which for its part is unsubstituted or substituted by halogen or C₁-C₄-alkoxy, furyl, thienyl, 1,3-dioxolanyl. Preference is furthermore given to C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl or phenyl, which is unsubstituted or substituted by 1 or 2 substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-fluoroalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, nitro and C₁-C₃-dialkylamino, naphthtyl or pyridyl. In a further preferred embodiment, R¹ and R² together form a five-, six- or seven-membered saturated or unsaturated nitrogen heterocycle which may contain a further heteroatom selected from the group consisting of N, a group NR⁶ (where R⁶ is as defined above) and O as ring member and/or may be substituted by one, two or three substituents selected from the group consisting of C₁-C₄-alkyl and C₁-C₄-haloalkyl.

In particularly preferred embodiment of the invention, one of the radicals R¹ or R² is hydrogen, C₁-C₆-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl and the other radical R¹ or R² is C₁-C₆-alkyl, C₃-C₈-cycloalkyl or phenyl.

The group Ar is in particular a group of the formula Ar-1

where

-   R^(a), R^(b), R^(c) and R^(d) independently of one another are     hydrogen, halogen, C₁-C₄-haloalkyl or cyano; -   * denotes the point of attachment of Ar to the C(O) group and -   ** denotes the point of attachment of Ar to the nitrogen atom of the     amino, nitro or iso(thio)cyanato group.

In a particularly preferred embodiment of the invention, the variables R^(a), R^(b), R^(c) and R^(d) are as defined below, in each case on their own or in combination:

-   R^(a) is halogen or cyano, in particular fluorine, chlorine or     cyano; -   R^(b) is hydrogen; -   R^(c) is halogen or hydrogen, in particular fluorine, chlorine or     hydrogen; -   R^(d) is hydrogen.

Accordingly, the present invention relates in particular to the preparation of the compounds IA,

where the variables R^(a), R^(b), R^(c), R^(d), A and W are as defined above.

In particular, the present invention relates to the preparation of the compounds IA.1 where A is NR¹R². Hereinbelow, these compounds are referred to as compounds IA.1.

The reaction of the compound II with phosgene, thiophosgene or diphosgene, hereinbelow also referred to as phosgenating agent, is usually carried out in an inert organic solvent. Suitable solvents for these reactions are—depending on the temperature range—hydrocarbons, such as pentane, hexane, cyclopentane, cyclohexane, toluene, xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene, ethers, such as 1,4-dioxane, anisole; glycol ethers, such as dimethyl glycol ether, diethyl glycol ether, diethylene glycol dimethyl ether; esters, such as ethyl acetate, propyl acetate, methyl isobutyrate, isobutyl acetate; carboxamides, such as N,N-dimethylformamide, N-methylpyrrolidone; nitrated hydrocarbons, such as nitrobenzene; tetraalkylureas such as tetraethylurea, tetrabutylurea, dimethylethyleneurea, dimethylpropyleneurea; nitriles, such as acetonitrile, propionitrile, butyronitrile or isobutyronitrile; or else mixtures of individual solvents.

If phosgene is used, preference is given to using a solvent which is substantially free of protic impurities such as water and alcohols. However, in the preparation of the isothiocyanates, it is also possible, similarly to Houben-Weyl, Methoden der organischen Chemie, 4th edition, Vol. IX, p. 875, to carry out the reaction of II with thiophosgene in a two-phase system comprising water and a water-immiscible organic solvent, or else in water.

In general, the compound II is initially charged in a reaction vessel, preferably as a solution or suspension in one of the solvents mentioned above, and the phosgenating agent is then added. The addition of the phosgenating agent is preferably carried out with stirring. The addition preferably takes place over a period of from 10 to 60 minutes. The phosgenating agent can be added as such or as a solution in one of the solvents mentioned above. In the case of phosgene, this is generally introduced into the solution or suspension.

The reaction temperature will generally not exceed 180° C., preferably 120° C. and in particular 100° C., and will generally be at least 40° C. and preferably at least 50° C. Frequently, at least the major part of the phosgenating agent will be added at a low temperature, for example in the range from 0 to 40° C., in particular from 10 to 40° C. and especially from 20 to 30° C., and the mixture will be heated during or after the addition to a temperature in the range from 40 to 180° C., in particular from 50 to 120° C. and especially from 70 to 100° C., until the reaction has gone to completion.

In general, from 0.9 to 2, preferably from 0.95 to 1.5, with particular preference from 0.98 to 1.09, molar equivalents of phosgenating agent are employed per mole of the compound II.

If appropriate, the conversion of II is carried out in the presence of a base. Suitable bases are, for example, basic inorganic compounds, for example alkali metal or alkaline earth metal hydroxides, bicarbonates or carbonates. However, the reaction can also be carried out in the presence of an organic base, for example a tertiary amine, such as triethylamine, tri-n-propylamine, N-ethyldiisopropylamine, pyridine, α-, β-, γ-picoline, 2,4-, 2,6-lutidine, N-methylpyrrolidine, dimethylaniline, N,N-dimethylcyclohexylamine, quinoline or acridine. The base (calculated as base equivalent) can be employed in substoichiometric, superstoichiometric or equimolar amounts, based on the compound II. In general, from 0.01 to 6 mol, preferably from 0.1 to 3 mol, of base are employed per mole of the compound II.

In another embodiment of the process according to the invention, the reaction is carried out in the presence of hydrogen chloride. In this case, the amount of hydrogen chloride is usually from 0.9 to 5.0 mol, preferably from 1.0 to 2.5 mol and in particular from 1.0 to 1.2 mol, of hydrogen chloride per mole of the compound II. The procedure usually adopted here is that the above-mentioned amount of gaseous hydrogen chloride is initially introduced into or a solution of hydrogen chloride in a solvent is initially added to a solution or suspension of the compound II in one of the abovementioned solvents, the phosgenating agent is then added in the manner described above and the reaction is then continued in the manner described above. The introduction of hydrogen chloride is usually carried out at temperatures from 10° C. to 60° C., preferably from 20° C. to 30° C.

If the process is carried out in the presence of hydrogen chloride, it is possible to use activated carbon as the catalyst. The amount of activated carbon is expediently from 1 to 10% by weight, preferably from 1 to 3% by weight, based on the weight of the compound II.

The reaction can be carried out at atmospheric pressure or under superatmospheric pressure, continuously or batch-wise. In general, the reaction of the compound II with a phosgenating agent will be carried out with exclusion of water. If appropriate, it may be advantageous to carry out the reaction under a protective atmosphere.

Work-up to isolate the target product can be carried out using the methods customary for this purpose. If the phosgenating agent used is phosgene, in general unreacted phosgene will initially be removed, for example by introducing a stream of nitrogen into the reaction mixture. The solvent is then removed by customary processes, for example by distillation. For further purification, it is possible to employ processes such as crystallization or chromatography, for example on silica gel. If appropriate, the residue can also be purified by trituration with a solvent, for example an aromatic hydrocarbon, such as benzene, toluene or xylene, or an aliphatic hydrocarbon, such as petroleum ether, hexane, cyclohexane, pentane, an ether, such as diethyl ether, etc., and mixtures of these.

The compounds of the formula II required as starting materials for carrying out the process according to the invention are likewise novel and, as interesting precursors, of importance for the process according to the invention. In the formula II, the variables Ar and A preferably denote those radicals which have already been mentioned in connection with the description of the compounds I according to the invention as being preferred for these substituents.

The compounds of the formula II can be obtained analogously to known processes for preparing anilines. The aniline compounds of the formula II can be prepared, for example, in accordance with Scheme 2 by initially reacting an aroyl compound of the formula III with a sulfamic acid amide IV in a condensation reaction to give an N-aroylsulfamic acid amide of the formula V, followed by reduction of the resulting N-aroylsulfamic acid amide V to give the compound II.

In Scheme 2, the variables A and Ar have the meanings given above, in particular the meanings given as being preferred. X is halogen, preferably chlorine, hydroxyl or a C₁-C₄-alkoxy group. The condensation of aroyl compounds of the formula III with sulfamic acid amides of the formula IV to give the corresponding benzoylsulfamides of the formula V is carried out similarly to known processes, for example as described in WO 01/83459, pp. 31-35, in the not yet published German patent application DE 102 21 910.0, the disclosure of which is hereby incorporated by way of reference.

The first reaction step is illustrated in more detail below:

If X in the formula III is hydroxyl, the carboxylic acid III is preferably initially activated by reaction with a coupling agent. The activated carboxylic acid III is then, generally without prior isolation, reacted with the sulfamic acid amide IV. Suitable coupling agents are, for example, N,N′-carbonyldiimidazole or carbodiimides, such as dicyclohexylcarbodiimide. These are generally employed in at least equimolar amount and up to a four-fold excess, based on the carboxylic acid III. If appropriate, the resulting reaction mixture of carboxylic acid III and coupling agent is heated and then allowed to cool to room temperature. The reaction is usually carried out in a solvent. Suitable solvents are, for example, chlorinated hydrocarbons, such as methylene chloride, 1,2-dichloroethane; ethers, for example dialkyl ethers, such as diethyl ether or methyl tert-butyl ether, or cyclic ethers, such as tetrahydrofuran or dioxane; carboxamides, such as dimethylformamide; N-methyllactams, such as N-methylpyrrolidone; nitriles, such as acetonitrile; aromatic hydrocarbons, such as toluene; aromatic amines, such as pyridine; or mixtures of these. This is followed by addition of the sulfamic acid amide IV. In general, the sulfamide IV is dissolved in the same solvent that is used for activating the carboxylic acid.

If X in the formula III is C₁-C₄-alkoxy, the esters can initially be converted according to known processes by hydrolysis in an acidic medium using strong mineral acids, such as concentrated hydrochloric acid or sulfuric acid, or organic acids, such as glacial acetic acid, or mixtures of these, into the corresponding carboxylic acids III. Alternatively, esters can also be hydrolyzed under alkaline conditions using bases such as alkali metal hydroxide, for example sodium hydroxide or potassium hydroxide, in the presence of water.

The carboxylic acids III (X═OH) can then be reacted in the manner described above or initially be converted into the acid chlorides (X═Cl) using a chlorinating agent, such as thionyl chloride or phosgene, followed by reaction of the acid chlorides with IV in the manner described below. The acid chlorides are prepared similarly to known processes, for example as described in EP 1 176 133 and WO 01/087872.

However, it is also possible to react the carboxylic acid ester of the formula III in which X is C₁-C₄-alkoxy directly with a sulfamic acid amide IV or a metal salt thereof in an amidation reaction with cleavage of the ester radical. The reaction is carried out similarly to the procedure described in Houben-Weyl, 4th edition, Vol. VIII, pp. 658-659.

If X in formula III is halogen, the aroyl compound III, preferably diluted in an inert solvent, will generally be added to the sulfamic acid amide of the formula IV, preferably likewise diluted in an inert solvent. It is, of course, also possible to initially charge the aroyl compound III and to add the sulfamic acid amide IV.

The molar ratios in which the starting materials III and IV are reacted with one another are generally from 0.9 to 1.2, preferably from 0.95 to 1.1, particularly preferably from 0.98 to 1.04, for the ratio of aroyl compound III to sulfamic acid amide IV.

The reaction is usually carried out at temperatures in the range from −30 to 100° C., preferably from −10 to 80° C., particularly preferably from 0 to 60° C.

The first reaction step is advantageously carried out under neutral conditions. If an acidic reaction product, for example hydrogen chloride (if X in formula III is halogen) is formed during the reaction, this is removed by addition of a basic compound. Suitable basic compounds include inorganic and organic bases. Suitable inorganic basic compounds are, for example, alkali metal or alkaline earth metal hydroxides, bicarbonates or carbonates. However, the reaction can also be carried out in the presence of an organic base, for example triethylamine, tri-n-propylamine, N-ethyldiisopropylamine, pyridine, α-, β-, γ-picoline, 2,4-, 2,6-lutidine, N-methylpyrrolidine, dimethylaniline, N,N-dimethylcyclohexylamine, quinoline or acridine. In general, an excess of base is employed, based on the compound III. The molar amount of base is from 1.0 to 2 mol, preferably from 1.02 to 1.3 mol, of base (calculated as base equivalent) per mole of the compound III. If appropriate, the reaction mixture contains pyridine or a pyridine compound, for example a 4-dialkylaminopyridine such as 4-dimethylaminopyridine, as catalyst. The added quantity of catalyst is about 0.1-10%, based on the compound III.

The reaction of the aroyl compounds III with the compounds of the formula IV is advantageously carried out in the presence of a solvent. Suitable solvents for these reactons are—depending on the temperature range—hydrocarbons, such as pentane, hexane, cyclopentane, cyclohexane, toluene, xylene, chlorinated hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene; ethers, such as 1,4-dioxane, anisole, glycol ethers, such as dimethyl glycol ether, diethyl glycol ether, diethylene glycol dimethyl ether; esters, such as ethyl acetate, propyl acetate, methyl isobutyrate, isobutyl acetate; carboxamides, such as N,N-dimethylformamide, N-methylpyrrolidone, nitrated hydrocarbons, such as nitrobenzene; tetraalkylureas, such as tetraethylurea, tetrabutylurea, dimethylethyleneurea, dimethylpropyleneurea; sulfoxides, such as dimethyl sulfoxide; sulfones, such as dimethyl sulfone, diethyl sulfone, tetramethylene sulfone; nitriles, such as acetonitrile, propionitrile, butyronitrile or isobutyronitrile; water; or else mixtures of individual solvents.

It is furthermore possible to carry out the reaction in an aqueous two-phase system, preferably in the presence of phase-transfer catalysts such as quaternary ammonium or phosphonium salts. Suitable reaction conditions for the two-phase reaction are those described in EP-A 556737.

Suitable for use as phase-transfer catalysts are quaternary ammonium or phosphonium salts. Suitable compounds which may be mentioned are the following: tetraalkyl-(C₁-C₁₈)-ammonium chlorides, bromides or fluorides, N-benzyltrialkyl-(C₁-C₁₈)-ammonium chlorides, bromides or fluorides, tetraalkyl-(C₁-C₁₈)-phosphonium chlorides or bromides, tetraphenylphosphonium chloride or bromide, (phenyl)_(o)(C₁-C₁₈-alkyl)_(p)-phosphonium chlorides or bromides, where o=1 to 3, p=3 to 1 and o+p=4. Particular preference is given to tetraethylammonium chloride and N-benzyltriethylammonium chloride. The amount of phase-transfer catalyst is generally up to 20% by weight, preferably from 1 to 15% by weight and particularly preferably from 2 to 8% by weight, based on the starting material IV.

The aroyl compound III is advantageously added over a period of from 0.25 to 2 hours to a mixture of the sulfamic acid amide IV and, if appropriate, the base in one of the above-mentioned solvents, and the mixture is stirred for another 0.5 to 16 hours, preferably 2 to 8 hours, until the reaction has gone to completion. The reaction temperature is generally from 0° C. to 60° C.

If an aqueous two-phase system is used, the starting materials III and IV can be added in any order with stirring to a mixture of the phase-transfer catalyst in the two phases, and the reaction can then be completed in the indicated temperature range by adding a base.

The reaction can be carried out continuously or batch-wise, at atmospheric pressure or under elevated pressure.

For work-up, the organic phase is extracted with dilute mineral acid such as hydrochloric acid, the organic phase is dried and the solvent is removed under reduced pressure. If appropriate, the residue can also be purified further by trituration with a solvent or solvent mixture, for example an aromatic hydrocarbon, such as benzene, xylene or toluene, or an aliphatic or cycloaliphatic hydrocarbon, such as petroleum ether, pentane, hexane or cyclohexane, an ether such as diethyl ether, etc., and mixtures of these, filtration with suction and drying.

The 2nd reaction step, i.e. the reduction of the nitro compound V to the compound II, is illustrated in more detail below.

The reduction of the compound V to the compound II can be effected, for example, using nascent hydrogen. To this end, the nitro compound is reacted with an acid in the presence of a base metal. According to their nature, base metals are dissolved by a Brönsted acid with evolution of hydrogen. Such metals generally have a normal potential of <0 V and in particular of ≦−0.1 V, for example in the range of from −0.1 to −1.0 V (in acidic aqueous solution at 15° C. and 1 bar). Examples of suitable metals are Zn, Fe and Sn, in particular Fe. Acids suitable for this purpose are both inorganic mineral acids, for example hydrochloric acid or dilute sulfuric acid, or mixtures of inorganic acid or one of the solvents mentioned above, for example gaseous HCl in an ether or an alcohol or a mixture thereof, and organic carboxylic acids, expediently acetic acid, propionic acid or butyric acid.

The reaction conditions correspond substantially to the reaction conditions used for reducing aliphatic or aromatic nitro groups to aliphatic or aromatic amino groups with nascent hydrogen (see, for example, H. Koopman, Rec. Tray. 80 (1961), 1075; see also N. Kornblum, L. Fischbein, J. Am. Chem. Soc. 77, (1955) 6266).

Depending on the type of metal and acid, the reaction temperature is generally in the range of from −20 to +120° C., with temperatures in the range of from 50 to 100° C. being preferred if alkanoic acids such as acetic acid are used. The reaction time can be from a few minutes to a number of hours, for example from about 20 minutes to 5 hours. Preferably, the compound V to be reduced is initially charged to the reaction vessel and the metal in question is then, preferably in finely divided form, in particular as a powder, added with mixing to the reaction mixture. The addition is preferably carried out over a period of from 10 minutes to 2 hours. It is, of course, also possible to initially charge the metal and the acid and to add the compound V, if appropriate together with an inert solvent. Frequently, the reaction mixture is allowed some extra reaction time at reaction temperature, for example from 10 minutes to 4 hours.

The reduction of V to II is preferably carried out using iron powder in dilute acid. Suitable acids are mineral acids, such as hydrochloric acid, or organic acids, such as formic acid, acetic acid, propionic acid, butyric acid. Preference is given to using acetic acid. The amount of iron powder is preferably from 2 to 5 mol, in particular from 2.5 to 4 mol, per mole of the compound V. The amount of acid is generally not critical. It is expedient to use an at least equimolar amount of acid, based on the nitro compound V, to reduce the starting material as completely as possible. The reaction can be carried out continuously or batch-wise. In this case, the reaction temperatures are in the range of from 50 to 100° C., preferably from 65 to 75° C. In one embodiment, for example, the iron powder is initially charged in acetic acid and the compound V is then added to the reaction vessel. The addition is preferably carried out over a period of from 20 to 60 minutes, with mixing of the components, for example by stirring. After the addition has ended, the mixture is allowed to react at reaction temperature for another 0.5 to 2 hours, preferably for about 1 hour. However, it is also possible to add the iron powder with stirring to the mixture of the compound V in glacial acetic acid and to bring the reaction to completion as described above.

Work-up for the isolation of the target product can be carried out by processes customary for this purpose. In general, the solvent is initially removed, for example by distillation. For further purification, it is possible to employ customary processes such as crystallization, chromatography, for example on silica gel, trituration with a solvent, for example an aromatic hydrocarbon, such as benzene, toluene or xylene, or an aliphatic hydrocarbon, such as petroleum ether, hexane, cyclohexane, pentane, a carboxylic ester, such as ethyl acetate, etc., and mixtures of these.

Suitable reducing agents are furthermore also metal hyrides and semimetal hydrides, such as aluminum hydride and hydrides derived therefrom, such as lithium aluminum hydride, diisobutylaluminum hydride; borohydrides, such as diborane and boranates derived therefrom, such as sodium borohydride or lithium borohydride. To this end, the nitro compound V is, in an inert solvent, brought into contact with the complex metal hydride at 10-65° C., advantageously at 20-50° C. The reaction time is preferably from 2 to 10 hours, advantageously from 3 to 6 hours. Reaction is preferably carried out in an organic solvent which is inert to the reducing agent. Suitable solvents are—depending on the chosen reducing agent—for example alcohols, e.g. C₁-C₄-alcohols, such as methanol, ethanol, n-propanol, isopropanol or n-butanol, and their mixtures with water, or ethers, such as diisopropyl ether, methyl tert-butyl ether, ethylene glycol dimethyl ether, dioxane or tetrahydrofuran.

In general, from 0.5 to 3, advantageously from 0.75 to 2.5, mol of metal hydride, semimetal hydride, borohydride or boranate are employed per mole of nitro compound V. The process follows the procedure described in Organikum, VEB Deutscher Verlag der Wissenschaften, Berlin 1976, 15th edition, pp. 612-616.

A further reducing agent suitable for converting the compound V into the compound II is hydrogen in the presence of catalytic amounts of transition metals or transition metal compounds, in particular those of the 8th transition group. Preferred transition metals are, for example, nickel, palladium, platinum, ruthenium or rhodium. The transition metals can be employed as such or in supported form. Examples of supports are activated carbon, alumina, ZrO₂, TiO₂, SiO₂, carbonates and the like. The transition metals can also be employed in the form of activated metals such as Raney nickel. The transition metals can also be used in the form of compounds. Suitable transition metal compounds are, for example, palladium oxide and platinum oxide. The catalysts are generally employed in an amount of from 0.05 to 10.0 mol % (calculated as metal), based on the compound V to be reduced. The reaction is carried out either in the absence of a solvent or in an inert solvent or diluent. Solvents or diluents suitable for the reaction are, depending on the solubility of the substrate to be hydrated and the chosen reducing agent, for example carboxylic acids, such as acetic acid, or aqueous solutions of organic acids, such as acetic acid and water, carboxylic acid esters, such as ethyl acetate, C₁-C₄-alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol or aromatic hydrocarbons, such as toluene. Following removal of the catalyst, the reaction solution can be worked up in a customary manner to afford the product. The hydration can be carried out at atmospheric pressure or under an elevated hydrogen pressure, for example at a hydrogen pressure of from 0.01 to 50 bar, preferably from 0.1 to 40 bar. For the catalytic hydration of aromatic nitro compounds, see, for example, Rylander in “Catalytic Hydrogenation over Platinum Metals”, Academic Press, New York, 1967, 168-202; Furst et al., Chem. Rev. 65 (1965), 52; Tepko et al., J. Org. Chem. 45, (1980), 4992.

In the case of chlorine-containing benzoylsulfamides, the hydration is, depending on the sensitivity of the substituents, carried out at from 20 to 170° C., expediently at from 20 to 140° C., advantageously at from 20 to 80° C. In the case of reactive halogen substituents, it is furthermore recommended to carry out the hydration in neutral solution, preferably at only slightly elevated pressure, using small amounts of nickel, platinum or else rhodium catalysts; also suitable are noble metal sulfides, such as platinum sulfide. The process is described in detail in Houben-Weyl, “Methoden der organischen Chemie”, Vol. IV/1C, pp. 520-526.

The reduction of the compound V to the compound II can also be carried out using sodium sulfide, advantageously in aqueous ammonia solution, in the presence of ammonium chloride, in accordance with the process described in Org. Syn., Coll. Vol., 3 (1955), 82. The reaction temperature is generally from 40 to 90° C., preferably from 60 to 80° C. Expediently, from 3 to 4 mol of sodium sulfide are employed per mol of nitro compound V.

The aroyl compounds III used in Scheme 2 can be obtained by processes known in the prior art or be prepared similarly to known processes, for example in accordance with U.S. Pat. No. 6,251,829, EP 415 641, EP 908 457, EP 1176133 and WO 01/087872.

The sulfamic acid amides IV are known in the prior art or can be prepared by known processes, for example in accordance with the German patent application DE 102 21 910.0 by reaction of ammonia with sulfamic acid halides. The disclosure of this publication is hereby incorporated by way of reference.

The sulfamic acid amides IV are preferably prepared by the process described in the not yet published German patent application DE 102 21 910.0. This process comprises the following steps: (i) reaction of a primary or secondary amine with an at least equimolar amount of SO₃ or an SO₃ source in the presence of at least equimolar amounts of a tertiary amine, based in each case on the primary or secondary amine, giving an amidosulfonic acid ammonium salt; (ii) reaction of the amidosulfonic acid ammonium salt with an at least stoichiometric amount of a phosphorus halide, giving a sulfamic acid halide, and (iii) reaction of the sulfamic acid halide obtained in step ii) with ammonia, giving the sulfamic acid amide V.

The process according to the invention allows, for the first time, the preparation of iso(thio)cyanatobenzoylsulfamic acid amides of the formula I. The compounds I are novel and also form part of the subject-matter of the present invention.

Among the iso(thio)cyanatobenzoylsulfamic acid amides of the formula I, preference is given to those of the formula IA, where the variables R^(a), R^(b), R^(c), R^(d) are as defined above.

Very particular preference is given to the compounds of the formula IA.1,

where the variables R¹, R², R^(a), R^(b), R^(c), R^(d) are as defined above.

Among the iso(thio)cyanatobenzoylsulfamic acid amides of the formula IA.1, particular preference is given to those in which the variables R¹, R², R^(a), R^(b), R^(c), R^(d) independently of one another, but preferably in combination, are as defined below:

-   R^(a) is cyano or halogen, in particular cyano, fluorine or     chlorine; -   R^(b) is hydrogen; -   R^(c) is hydrogen or halogen, in particular hydrogen, fluorine or     chlorine; -   R^(d) is hydrogen; -   R¹ and R² independently of one another are hydrogen, C₁-C₆-alkyl     which is optionally substituted by a substituent selected from the     group consisting of halogen, cyano, C₁-C₄-alkoxy,     C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₃-C₈-cycloalkyl, furyl,     thienyl, 1,3-dioxolanyl, phenyl which for its part is optionally     substituted by halogen or C₁-C₄-alkoxy,     -   C₂-C₆-alkenyl, C₂-C₆-alkynyl, C₃-C₈-cycloalkyl or phenyl which         is optionally substituted by 1 or 2 substituents selected from         the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-fluoroalkyl,         C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, nitro and         C₁-C₃-dialkylamino, naphthtyl or pyridyl or -   R¹ and R² together form a five-, six- or seven-membered saturated or     unsaturated nitrogen heterocycle which may optionally contain a     further heteroatom selected from the group consisting of N, a group     NR⁶ (where R⁶ is as defined above) and O as ring member and/or which     may be substituted by one, two or three substituents selected from     the group consisting of C₁-C₄-alkyl and C₁-C₄-halogenalkyl.     -   In particular, one of the radicals R¹ or R² is hydrogen,         C₁-C₈-alkyl, C₂-C₆-alkenyl or C₂-C₆-alkynyl and the other         radical R¹ or R² is C₁-C₈-alkyl, C₃-C₈-cycloalkyl or phenyl.

Very particular preference is given to the isocyanatobenzoylsulfamic acid amides of the formula IA.1-a (≡I where W=oxygen, Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)═F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-a.1 to IA.1-a.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

TABLE 1 (IA.1-a)

No. R¹ R² 1 H CH₃ 2 H C₂H₅ 3 H CH₂CH₂—Cl 4 H CH₂CH₂—CN 5 H CH₂—CO—OCH₃ 6 H CH₂—CO—OC₂H₅ 7 H CH(CH₃)—CO—OCH₃ 8 H CH₂CH₂—OCH₃ 9 H CH₂—C₂H₅ 10 H CH₂CH₂—C₂H₅ 11 H CH(CH₃)₂ 12 H CH(CH₃)—C₂H₅ 13 H CH₂—CH(CH₃)₂ 14 H C(CH₃)₃ 15 H CH(CH₃)—CH₂—C₂H₅ 16 H CH₂—CH(CH₃)—C₂H₅ 17 H CH₂CH₂—CH(CH₃)₂ 18 H CH₂—CH═CH₂ 19 H CH(CH₃)═CH₂ 20 H CH₂═CH—CH₃ 21 H CH₂—C≡CH 22 H CH(CH₃)—C≡CH 23 H cyclopropyl 24 H CH₂-cyclopropyl 25 H cyclopentyl 26 H CH₂-cyclopentyl 27 H CH₂-(1,3-dioxolan-2-yl) 28 H CH₂-(2-furyl) 29 H CH₂-(3-furyl) 30 H CH₂-(2-thienyl) 31 H CH₂-(3-thienyl) 32 H phenyl 33 H 2-chlorophenyl 34 H 3-chlorophenyl 35 H 4-chlorophenyl 36 H 2-fluorophenyl 37 H 3-fluorophenyl 38 H 4-fluorophenyl 39 H 2-methylphenyl 40 H 3-methylphenyl 41 H 4-methylphenyl 42 H 2-methoxyphenyl 43 H 3-methoxyphenyl 44 H 4-methoxyphenyl 45 H 2-(methoxycarbonyl)phenyl 46 H 3-(methoxycarbonyl)phenyl 47 H 4-(methoxycarbonyl)phenyl 48 H 2-nitrophenyl 49 H 3-nitrophenyl 50 H 4-nitrophenyl 51 H 2-(dimethylamino)phenyl 52 H 3-(dimethylamino)phenyl 53 H 4-(dimethylamino)phenyl 54 H 2-(trifluoromethyl)phenyl 55 H 3-(trifluoromethyl)phenyl 56 H 4-(trifluoromethyl)phenyl 57 H 3-(phenoxy)phenyl 58 H 4-(phenoxy)phenyl 59 H 2,4-difluorophenyl 60 H 2,4-dichlorophenyl 61 H 3,4-difluorophenyl 62 H 3,4-dichlorophenyl 63 H 3,5-difluorophenyl 64 H 3,5-dichlorophenyl 65 H 2-pyridyl 66 H 3-pyridyl 67 H 4-pyridyl 68 H α-naphthyl 69 H benzyl 70 H 2-chlorobenzyl 71 H 3-chlorobenzyl 72 H 4-chlorobenzyl 73 H 2-methoxybenzyl 74 H 3-methoxybenzyl 75 H 4-methoxybenzyl 76 CH₃ CH₃ 77 CH₃ C₂H₅ 78 CH₃ CH₂CH₂—Cl 79 CH₃ CH₂CH₂—CN 80 CH₃ CH₂—CO—OCH₃ 81 CH₃ CH₂—CO—OC₂H₅ 82 CH₃ CH(CH₃)—CO—OCH₃ 83 CH₃ CH₂CH₂—OCH₃ 84 CH₃ CH₂—C₂H₅ 85 CH₃ CH₂CH₂—C₂H₅ 86 CH₃ CH(CH₃)₂ 87 CH₃ CH(CH₃)—C₂H₅ 88 CH₃ CH₂—CH(CH₃)₂ 89 CH₃ C(CH₃)₃ 90 CH₃ CH(CH₃)—CH₂—C₂H₅ 91 CH₃ CH₂—CH(CH₃)—C₂H₅ 92 CH₃ CH₂CH₂—CH(CH₃)₂ 93 CH₃ CH₂—CH═CH₂ 94 CH₃ CH(CH₃)═CH₂ 95 CH₃ CH₂═CH—CH₃ 96 CH₃ CH₂—C≡CH 97 CH₃ CH(CH₃)—C≡CH 98 CH₃ cyclopropyl 99 CH₃ CH₂-cyclopropyl 100 CH₃ cyclopentyl 101 CH₃ CH₂-cyclopentyl 102 CH₃ CH₂-(1,3-dioxolan-2-yl) 103 CH₃ CH₂-(2-furyl) 104 CH₃ CH₂-(3-furyl) 105 CH₃ CH₂-(2-thienyl) 106 CH₃ CH₂-(3-thienyl) 107 CH₃ phenyl 108 CH₃ 2-chlorophenyl 109 CH₃ 3-chlorophenyl 110 CH₃ 4-chlorophenyl 111 CH₃ 2-fluorophenyl 112 CH₃ 3-fluorophenyl 113 CH₃ 4-fluorophenyl 114 CH₃ 2-methylphenyl 115 CH₃ 3-methylphenyl 116 CH₃ 4-methylphenyl 117 CH₃ 2-methoxyphenyl 118 CH₃ 3-methoxyphenyl 119 CH₃ 4-methoxyphenyl 120 CH₃ 2-(methoxycarbonyl)phenyl 121 CH₃ 3-(methoxycarbonyl)phenyl 122 CH₃ 4-(methoxycarbonyl)phenyl 123 CH₃ 2-nitrophenyl 124 CH₃ 3-nitrophenyl 125 CH₃ 4-nitrophenyl 126 CH₃ 2-(dimethylamino)phenyl 127 CH₃ 3-(dimethylamino)phenyl 128 CH₃ 4-(dimethylamino)phenyl 129 CH₃ 2-(trifluoromethyl)phenyl 130 CH₃ 3-(trifluoromethyl)phenyl 131 CH₃ 4-(trifluoromethyl)phenyl 132 CH₃ 3-(phenoxy)phenyl 133 CH₃ 4-(phenoxy)phenyl 134 CH₃ 2,4-difluorophenyl 135 CH₃ 2,4-dichlorophenyl 136 CH₃ 3,4-difluorophenyl 137 CH₃ 3,4-dichlorophenyl 138 CH₃ 3,5-difluorophenyl 139 CH₃ 3,5-dichlorophenyl 140 CH₃ 2-pyridyl 141 CH₃ 3-pyridyl 142 CH₃ 4-pyridyl 143 CH₃ α-naphthyl 144 CH₃ benzyl 145 CH₃ 2-chlorobenzyl 146 CH₃ 3-chlorobenzyl 147 CH₃ 4-chlorobenzyl 148 CH₃ 2-methoxybenzyl 149 CH₃ 3-methoxybenzyl 150 CH₃ 4-methoxybenzyl 151 C₂H₅ C₂H₅ 152 C₂H₅ CH₂CH₂—Cl 153 C₂H₅ CH₂CH₂—CN 154 C₂H₅ CH₂—CO—OCH₃ 155 C₂H₅ CH₂—CO—OC₂H₅ 156 C₂H₅ CH(CH₃)—CO—OCH₃ 157 C₂H₅ CH₂CH₂—OCH₃ 158 C₂H₅ CH₂—C₂H₅ 159 C₂H₅ CH₂CH₂—C₂H₅ 160 C₂H₅ CH(CH₃)₂ 161 C₂H₅ CH(CH₃)—C₂H₅ 162 C₂H₅ CH₂—CH(CH₃)₂ 163 C₂H₅ C(CH₃)₃ 164 C₂H₅ CH(CH₃)—CH₂—C₂H₅ 165 C₂H₅ CH₂—CH(CH₃)—C₂H₅ 166 C₂H₅ CH₂CH₂—CH(CH₃)₂ 167 C₂H₅ CH₂—CH═CH₂ 168 C₂H₅ CH(CH₃)═CH₂ 169 C₂H₅ CH₂═CH—CH₃ 170 C₂H₅ CH₂—C≡CH 171 C₂H₅ CH(CH₃)—C≡CH 172 C₂H₅ cyclopropyl 173 C₂H₅ CH₂-cyclopropyl 174 C₂H₅ cyclopentyl 175 C₂H₅ CH₂-cyclopentyl 176 C₂H₅ CH₂-(1,3-dioxolan-2-yl) 177 C₂H₅ CH₂-(2-furyl) 178 C₂H₅ CH₂-(3-furyl) 179 C₂H₅ CH₂-(2-thienyl) 180 C₂H₅ CH₂-(3-thienyl) 181 C₂H₅ phenyl 182 C₂H₅ 2-chlorophenyl 183 C₂H₅ 3-chlorophenyl 184 C₂H₅ 4-chlorophenyl 185 C₂H₅ 2-fluorophenyl 186 C₂H₅ 3-fluorophenyl 187 C₂H₅ 4-fluorophenyl 188 C₂H₅ 2-methylphenyl 189 C₂H₅ 3-methylphenyl 190 C₂H₅ 4-methylphenyl 191 C₂H₅ 2-methoxyphenyl 192 C₂H₅ 3-methoxyphenyl 193 C₂H₅ 4-methoxyphenyl 194 C₂H₅ 2-(methoxycarbonyl)phenyl 195 C₂H₅ 3-(methoxycarbonyl)phenyl 196 C₂H₅ 4-(methoxycarbonyl)phenyl 197 C₂H₅ 2-nitrophenyl 198 C₂H₅ 3-nitrophenyl 199 C₂H₅ 4-nitrophenyl 200 C₂H₅ 2-(dimethylamino)phenyl 201 C₂H₅ 3-(dimethylamino)phenyl 202 C₂H₅ 4-(dimethylamino)phenyl 203 C₂H₅ 2-(trifluoromethyl)phenyl 204 C₂H₅ 3-(trifluoromethyl)phenyl 205 C₂H₅ 4-(trifluoromethyl)phenyl 206 C₂H₅ 3-(phenoxy)phenyl 207 C₂H₅ 4-(phenoxy)phenyl 208 C₂H₅ 2,4-difluorophenyl 209 C₂H₅ 2,4-dichlorophenyl 210 C₂H₅ 3,4-difluorophenyl 211 C₂H₅ 3,4-dichlorophenyl 212 C₂H₅ 3,5-difluorophenyl 213 C₂H₅ 3,5-dichlorophenyl 214 C₂H₅ 2-pyridyl 215 C₂H₅ 3-pyridyl 216 C₂H₅ 4-pyridyl 217 C₂H₅ α-naphthyl 218 C₂H₅ benzyl 219 C₂H₅ 2-chlorobenzyl 220 C₂H₅ 3-chlorobenzyl 221 C₂H₅ 4-chlorobenzyl 222 C₂H₅ 2-methoxybenzyl 223 C₂H₅ 3-methoxybenzyl 224 C₂H₅ 4-methoxybenzyl 225 CH₂—C₂H₅ C₂H₅ 226 CH₂—C₂H₅ CH₂CH₂—Cl 227 CH₂—C₂H₅ CH₂CH₂—CN 228 CH₂—C₂H₅ CH₂—CO—OCH₃ 229 CH₂—C₂H₅ CH₂—CO—OC₂H₅ 230 CH₂—C₂H₅ CH(CH₃)—CO—OCH₃ 231 CH₂—C₂H₅ CH₂CH₂—OCH₃ 232 CH₂—C₂H₅ CH₂—C₂H₅ 233 CH₂—C₂H₅ CH₂CH₂—C₂H₅ 234 CH₂—C₂H₅ CH(CH₃)₂ 235 CH₂—C₂H₅ CH(CH₃)—C₂H₅ 236 CH₂—C₂H₅ CH₂—CH(CH₃)₂ 237 CH₂—C₂H₅ C(CH₃)₃ 238 CH₂—C₂H₅ CH(CH₃)—CH₂—C₂H₅ 239 CH₂—C₂H₅ CH₂—CH(CH₃)—C₂H₅ 240 CH₂—C₂H₅ CH₂CH₂—CH(CH₃)₂ 241 CH₂—C₂H₅ CH₂—CH═CH₂ 242 CH₂—C₂H₅ CH(CH₃)═CH₂ 243 CH₂—C₂H₅ CH₂═CH—CH₃ 244 CH₂—C₂H₅ CH₂—C≡CH 245 CH₂—C₂H₅ CH(CH₃)—C≡CH 246 CH₂—C₂H₅ cyclopropyl 247 CH₂—C₂H₅ CH₂-cyclopropyl 248 CH₂—C₂H₅ cyclopentyl 249 CH₂—C₂H₅ CH₂-cyclopentyl 250 CH₂—C₂H₅ CH₂-(1,3-dioxolan-2-yl) 251 CH₂—C₂H₅ CH₂-(2-furyl) 252 CH₂—C₂H₅ CH₂-(3-furyl) 253 CH₂—C₂H₅ CH₂-(2-thienyl) 254 CH₂—C₂H₅ CH₂-(3-thienyl) 255 CH₂—C₂H₅ phenyl 256 CH₂—C₂H₅ 2-chlorophenyl 257 CH₂—C₂H₅ 3-chlorophenyl 258 CH₂—C₂H₅ 4-chlorophenyl 259 CH₂—C₂H₅ 2-fluorophenyl 260 CH₂—C₂H₅ 3-fluorophenyl 261 CH₂—C₂H₅ 4-fluorophenyl 262 CH₂—C₂H₅ 2-methylphenyl 263 CH₂—C₂H₅ 3-methylphenyl 264 CH₂—C₂H₅ 4-methylphenyl 265 CH₂—C₂H₅ 2-methoxyphenyl 266 CH₂—C₂H₅ 3-methoxyphenyl 267 CH₂—C₂H₅ 4-methoxyphenyl 268 CH₂—C₂H₅ 2-(methoxycarbonyl)phenyl 269 CH₂—C₂H₅ 3-(methoxycarbonyl)phenyl 270 CH₂—C₂H₅ 4-(methoxycarbonyl)phenyl 271 CH₂—C₂H₅ 2-nitrophenyl 272 CH₂—C₂H₅ 3-nitrophenyl 273 CH₂—C₂H₅ 4-nitrophenyl 274 CH₂—C₂H₅ 2-(dimethylamino)phenyl 275 CH₂—C₂H₅ 3-(dimethylamino)phenyl 276 CH₂—C₂H₅ 4-(dimethylamino)phenyl 277 CH₂—C₂H₅ 2-(trifluoromethyl)phenyl 278 CH₂—C₂H₅ 3-(trifluoromethyl)phenyl 279 CH₂—C₂H₅ 4-(trifluoromethyl)phenyl 280 CH₂—C₂H₅ 3-(phenoxy)phenyl 281 CH₂—C₂H₅ 4-(phenoxy)phenyl 282 CH₂—C₂H₅ 2,4-difluorophenyl 283 CH₂—C₂H₅ 2,4-dichlorophenyl 284 CH₂—C₂H₅ 3,4-difluorophenyl 285 CH₂—C₂H₅ 3,4-dichlorophenyl 286 CH₂—C₂H₅ 3,5-difluorophenyl 287 CH₂—C₂H₅ 3,5-dichlorophenyl 288 CH₂—C₂H₅ 2-pyridyl 289 CH₂—C₂H₅ 3-pyridyl 290 CH₂—C₂H₅ 4-pyridyl 291 CH₂—C₂H₅ α-naphthyl 292 CH₂—C₂H₅ benzyl 293 CH₂—C₂H₅ 2-chlorobenzyl 294 CH₂—C₂H₅ 3-chlorobenzyl 295 CH₂—C₂H₅ 4-chlorobenzyl 296 CH₂—C₂H₅ 2-methoxybenzyl 297 CH₂—C₂H₅ 3-methoxybenzyl 298 CH₂—C₂H₅ 4-methoxybenzyl 299 CH₂—CH₂—C₂H₅ CH₂CH₂—Cl 300 CH₂—CH₂—C₂H₅ CH₂CH₂—CN 301 CH₂—CH₂—C₂H₅ CH₂—CO—OCH₃ 302 CH₂—CH₂—C₂H₅ CH₂—CO—OC₂H₅ 303 CH₂—CH₂—C₂H₅ CH(CH₃)—CO—OCH₃ 304 CH₂—CH₂—C₂H₅ CH₂CH₂—OCH₃ 305 CH₂—CH₂—C₂H₅ CH₂CH₂—C₂H₅ 306 CH₂—CH₂—C₂H₅ CH(CH₃)₂ 307 CH₂—CH₂—C₂H₅ CH(CH₃)—C₂H₅ 308 CH₂—CH₂—C₂H₅ CH₂—CH(CH₃)₂ 309 CH₂—CH₂—C₂H₅ C(CH₃)₃ 310 CH₂—CH₂—C₂H₅ CH(CH₃)—CH₂—C₂H₅ 311 CH₂—CH₂—C₂H₅ CH₂—CH(CH₃)—C₂H₅ 312 CH₂—CH₂—C₂H₅ CH₂CH₂—CH(CH₃)₂ 313 CH₂—CH₂—C₂H₅ CH₂—CH═CH₂ 314 CH₂—CH₂—C₂H₅ CH(CH₃)═CH₂ 315 CH₂—CH₂—C₂H₅ CH₂═CH—CH₃ 316 CH₂—CH₂—C₂H₅ CH₂—C≡CH 317 CH₂—CH₂—C₂H₅ CH(CH₃)—C≡CH 318 CH₂—CH₂—C₂H₅ cyclopropyl 319 CH₂—CH₂—C₂H₅ CH₂-cyclopropyl 320 CH₂—CH₂—C₂H₅ cyclopentyl 321 CH₂—CH₂—C₂H₅ CH₂-cyclopentyl 322 CH₂—CH₂—C₂H₅ CH₂-(1,3-dioxolan-2-yl) 323 CH₂—CH₂—C₂H₅ CH₂-(2-furyl) 324 CH₂—CH₂—C₂H₅ CH₂-(3-furyl) 325 CH₂—CH₂—C₂H₅ CH₂-(2-thienyl) 326 CH₂—CH₂—C₂H₅ CH₂-(3-thienyl) 327 CH₂—CH₂—C₂H₅ phenyl 328 CH₂—CH₂—C₂H₅ 2-chlorophenyl 329 CH₂—CH₂—C₂H₅ 3-chlorophenyl 330 CH₂—CH₂—C₂H₅ 4-chlorophenyl 331 CH₂—CH₂—C₂H₅ 2-fluorophenyl 332 CH₂—CH₂—C₂H₅ 3-fluorophenyl 333 CH₂—CH₂—C₂H₅ 4-fluorophenyl 334 CH₂—CH₂—C₂H₅ 2-methylphenyl 335 CH₂—CH₂—C₂H₅ 3-methylphenyl 336 CH₂—CH₂—C₂H₅ 4-methylphenyl 337 CH₂—CH₂—C₂H₅ 2-methoxyphenyl 338 CH₂—CH₂—C₂H₅ 3-methoxyphenyl 339 CH₂—CH₂—C₂H₅ 4-methoxyphenyl 340 CH₂—CH₂—C₂H₅ 2-(methoxycarbonyl)phenyl 341 CH₂—CH₂—C₂H₅ 3-(methoxycarbonyl)phenyl 342 CH₂—CH₂—C₂H₅ 4-(methoxycarbonyl)phenyl 343 CH₂—CH₂—C₂H₅ 2-nitrophenyl 344 CH₂—CH₂—C₂H₅ 3-nitrophenyl 345 CH₂—CH₂—C₂H₅ 4-nitrophenyl 346 CH₂—CH₂—C₂H₅ 2-(dimethylamino)phenyl 347 CH₂—CH₂—C₂H₅ 3-(dimethylamino)phenyl 348 CH₂—CH₂—C₂H₅ 4-(dimethylamino)phenyl 349 CH₂—CH₂—C₂H₅ 2-(trifluoromethyl)phenyl 350 CH₂—CH₂—C₂H₅ 3-(trifluoromethyl)phenyl 351 CH₂—CH₂—C₂H₅ 4-(trifluoromethyl)phenyl 352 CH₂—CH₂—C₂H₅ 3-(phenoxy)phenyl 353 CH₂—CH₂—C₂H₅ 4-(phenoxy)phenyl 354 CH₂—CH₂—C₂H₅ 2,4-difluorophenyl 355 CH₂—CH₂—C₂H₅ 2,4-dichlorophenyl 356 CH₂—CH₂—C₂H₅ 3,4-difluorophenyl 357 CH₂—CH₂—C₂H₅ 3,4-dichlorophenyl 358 CH₂—CH₂—C₂H₅ 3,5-difluorophenyl 359 CH₂—CH₂—C₂H₅ 3,5-dichlorophenyl 360 CH₂—CH₂—C₂H₅ 2-pyridyl 361 CH₂—CH₂—C₂H₅ 3-pyridyl 362 CH₂—CH₂—C₂H₅ 4-pyridyl 363 CH₂—CH₂—C₂H₅ α-naphthyl 364 CH₂—CH₂—C₂H₅ benzyl 365 CH₂—CH₂—C₂H₅ 2-chlorobenzyl 366 CH₂—CH₂—C₂H₅ 3-chlorobenzyl 367 CH₂—CH₂—C₂H₅ 4-chlorobenzyl 368 CH₂—CH₂—C₂H₅ 2-methoxybenzyl 369 CH₂—CH₂—C₂H₅ 3-methoxybenzyl 370 CH₂—CH₂—C₂H₅ 4-methoxybenzyl 371 CH(CH₃)₂ CH₂CH₂—Cl 372 CH(CH₃)₂ CH₂CH₂—CN 373 CH(CH₃)₂ CH₂—CO—OCH₃ 374 CH(CH₃)₂ CH₂—CO—OC₂H₅ 375 CH(CH₃)₂ CH(CH₃)—CO—OCH₃ 376 CH(CH₃)₂ CH₂CH₂—OCH₃ 377 CH(CH₃)₂ CH(CH₃)₂ 378 CH(CH₃)₂ CH(CH₃)—C₂H₅ 379 CH(CH₃)₂ CH₂—CH(CH₃)₂ 380 CH(CH₃)₂ C(CH₃)₃ 381 CH(CH₃)₂ CH(CH₃)—CH₂—C₂H₅ 382 CH(CH₃)₂ CH₂—CH(CH₃)—C₂H₅ 383 CH(CH₃)₂ CH₂CH₂—CH(CH₃)₂ 384 CH(CH₃)₂ CH₂—CH═CH₂ 385 CH(CH₃)₂ CH(CH₃) ═CH₂ 386 CH(CH₃)₂ CH₂═CH—CH₃ 387 CH(CH₃)₂ CH₂—C≡CH 388 CH(CH₃)₂ CH(CH₃)—C≡CH 389 CH(CH₃)₂ cyclopropyl 390 CH(CH₃)₂ CH₂-cyclopropyl 391 CH(CH₃)₂ cyclopentyl 392 CH(CH₃)₂ CH₂-cyclopentyl 393 CH(CH₃)₂ CH₂-(1,3-dioxolan-2-yl) 394 CH(CH₃)₂ CH₂-(2-furyl) 395 CH(CH₃)₂ CH₂-(3-furyl) 396 CH(CH₃)₂ CH₂-(2-thienyl) 397 CH(CH₃)₂ CH₂-(3-thienyl) 398 CH(CH₃)₂ phenyl 399 CH(CH₃)₂ 2-chlorophenyl 400 CH(CH₃)₂ 3-chlorophenyl 401 CH(CH₃)₂ 4-chlorophenyl 402 CH(CH₃)₂ 2-fluorophenyl 403 CH(CH₃)₂ 3-fluorophenyl 404 CH(CH₃)₂ 4-fluorophenyl 405 CH(CH₃)₂ 2-methylphenyl 406 CH(CH₃)₂ 3-methylphenyl 407 CH(CH₃)₂ 4-methylphenyl 408 CH(CH₃)₂ 2-methoxyphenyl 409 CH(CH₃)₂ 3-methoxyphenyl 410 CH(CH₃)₂ 4-methoxyphenyl 411 CH(CH₃)₂ 2-(methoxycarbonyl)phenyl 412 CH(CH₃)₂ 3-(methoxycarbonyl)phenyl 413 CH(CH₃)₂ 4-(methoxycarbonyl)phenyl 414 CH(CH₃)₂ 2-nitrophenyl 415 CH(CH₃)₂ 3-nitrophenyl 416 CH(CH₃)₂ 4-nitrophenyl 417 CH(CH₃)₂ 2-(dimethylamino)phenyl 418 CH(CH₃)₂ 3-(dimethylamino)phenyl 419 CH(CH₃)₂ 4-(dimethylamino)phenyl 420 CH(CH₃)₂ 2-(trifluoromethyl)phenyl 421 CH(CH₃)₂ 3-(trifluoromethyl)phenyl 422 CH(CH₃)₂ 4-(trifluoromethyl)phenyl 423 CH(CH₃)₂ 3-(phenoxy)phenyl 424 CH(CH₃)₂ 4-(phenoxy)phenyl 425 CH(CH₃)₂ 2,4-difluorophenyl 426 CH(CH₃)₂ 2,4-dichlorophenyl 427 CH(CH₃)₂ 3,4-difluorophenyl 428 CH(CH₃)₂ 3,4-dichlorophenyl 429 CH(CH₃)₂ 3,5-difluorophenyl 430 CH(CH₃)₂ 3,5-dichlorophenyl 431 CH(CH₃)₂ 2-pyridyl 432 CH(CH₃)₂ 3-pyridyl 433 CH(CH₃)₂ 4-pyridyl 434 CH(CH₃)₂ α-naphthyl 435 CH(CH₃)₂ benzyl 436 CH(CH₃)₂ 2-chlorobenzyl 437 CH(CH₃)₂ 3-chlorobenzyl 438 CH(CH₃)₂ 4-chlorobenzyl 439 CH(CH₃)₂ 2-methoxybenzyl 440 CH(CH₃)₂ 3-methoxybenzyl 441 CH(CH₃)₂ 4-methoxybenzyl 442 —(CH₂)₄— 443 —CH₂—CH═CH—CH₂— 444 H cyclohexyl 445 CH₃ cyclohexyl 446 C₂H₅ cyclohexyl 447 n-C₃H₇ cyclohexyl 448 i-C₃H₇ cyclohexyl 449 n-C₄H₉ cyclohexyl 450 i-C₄H₉ cyclohexyl 451 sec-C₄H₉ cyclohexyl 452 tert-C₄H₉ cyclohexyl 453 H CH₂—CH═CH—CH₃ 454 CH₃ CH₂—CH═CH—CH₃ 455 C₂H₅ CH₂—CH═CH—CH₃ 456 n-C₃H₇ CH₂—CH═CH—CH₃ 457 i-C₃H₇ CH₂—CH═CH—CH₃ 458 n-C₄H₉ CH₂—CH═CH—CH₃ 459 i-C₄H₉ CH₂—CH═CH—CH₃ 460 sec-C₄H₉ CH₂—CH═CH—CH₃ 461 tert-C₄H₉ CH₂—CH═CH—CH₃ 462 H CH₃S—CH₂CH₂ 463 CH₃ CH₃S—CH₂CH₂ 464 C₂H₅ CH₃S—CH₂CH₂ 465 n-C₃H₇ CH₃S—CH₂CH₂ 466 i-C₃N₇ CH₃S—CH₂CH₂ 467 n-C₄H₉ CH₃S—CH₂CH₂ 468 i-C₄H₉ CH₃S—CH₂CH₂ 469 sec-C₄H₉ CH₃S—CH₂CH₂ 470 tert-C₄H₉ CH₃S—CH₂CH₂ 471 H C₂H₅—O—CH₂CH₂ 472 CH₃ C₂H₅—O—CH₂CH₂ 473 C₂H₅ C₂H₅—O—CH₂CH₂ 474 n-C₃H₇ C₂H₅—O—CH₂CH₂ 475 i-C₃H₇ C₂H₅—O—CH₂CH₂ 476 n-C₄H₉ C₂H₅—O—CH₂CH₂ 477 i-C₄H₉ C₂H₅—O—CH₂CH₂ 478 sec-C₄H₉ C₂H₅—O—CH₂CH₂ 479 tert-C₄H₉ C₂H₅—O—CH₂CH₂ 480 CH₂CH₂—O—CH₂CH₂ 481 CH₂—CH═CH—CH₂ 482 CH═CH—CH₂—CH₂ 483 CH₂—CH₂—CH₂—CH₂—CH₂ 484 CH₂—CH₂—O—CH(CH₃)—CH₂ 485 CH₂—CH₂—O—CH₂—CH(CH₃) 486 CH₂—CH₂—N(CH₃)—CH₂—CH₂ 487 CH₂—CH(CH₃)—O—CH(CH₃)—CH₂ 488 CH₂—CH═CH—CH₂—CH₂ 489 CH═CH—CH₂—CH₂—CH₂ 490 CH₂—CH₂—CH₂—CH₂—CH(CH₃) 491 CH₂—CH₂—CH₂—CH(CH₃)—CH₂ 492 CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 493 CH₂—CH₂—CH₂—CH₂—CH(CH₂CH₂Cl) 494 CH₂—CH₂—CH₂—CH(CH₂CH₂Cl)—CH₂ 495 CH₂—CH₂—CH(CH₂CH₂Cl)—CH₂—CH₂

Very particular preference is given to the isocyanatobenzoylsulfamic acid amides of the formula IA.1-b (≡I where W=oxygen, Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=H, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-b.1 to IA.1-b.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isocyanatobenzoylsulfamic acid amides of the formula IA.1-c (≡I where W=oxygen, Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-c.1 to IA.1-c.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isocyanatobenzoylsulfamic acid amides of the formula IA.1-d (≡I where W=oxygen, Ar=Ar-1 where R^(a)=F and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²) where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-d.1 to IA.1-d.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isocyanatobenzoylsulfamic acid amides of the formula IA.1-e (≡I where W=oxygen, Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-e.1 to IA.1-e.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isocyanatobenzoylsulfamic acid amides of the formula IA.1-f (≡I where W=oxygen, Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-f.1 to IA.1-f.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isothiocyanatobenzoylsulfamic acid amides of the formula IA.1-g (≡I where W=sulfur, Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-g.1 to IA.1-g.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isothiocyanatobenzoylsulfamic acid amides of the formula IA.1-h (≡I where W=sulfur, Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=H, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-h.1 to IA.1-h.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isothiocyanatobenzoylsulfamic acid amides of the formula IA.1-i (≡I where W=sulfur, Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-1.1 to IA.1-1.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isothiocyanatobenzoylsulfamic acid amides of the formula IA.1-j (≡I where W=sulfur, Ar=Ar-1 where R^(a)=F and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-j.1 to IA.1-j.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isothiocyanatobenzoylsulfamic acid amides of the formula IA.1-k (≡I where W=sulfur, Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-k.1 to IA.1-k.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the isothiocyanatobenzoylsulfamic'acid amides of the formula IA.1-1 (≡I where W=sulfur, Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IA.1-1.1 to IA.1-1.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

In the process according to the invention, the starting materials used are aminobenzoylsulfamic acid amides of the formula II. These compounds are likewise novel and represent useful intermediates for preparing the iso(thio)cyanatobenzoylsulfamic acid amides I. With respect to the preparation process, reference is made to what has been said above.

Accordingly, the present invention also relates to the aniline compounds of the formula II, in particular to compounds of the formula IIA (≡I where Ar=Ar-1),

where R^(a), R^(b), R^(c), R^(d) and A are as defined above. In the formula IIA, R^(a), R^(b), R^(c), R^(d) and A preferably denote those radicals which have already been mentioned in connection with the description of the compounds I according to the invention as being preferred for these variables.

Particular preference is given to the compounds of the formula IIA.1,

in which the variables R¹¹, R², R^(a), R^(b), R^(e), R^(d) are as defined above. In the formula IIA.1, the variables R¹, R², R^(a), R^(b), R^(e), R^(d) preferably have those meanings which have already been mentioned in connection with the description of the compounds IA.1 according to the invention as being preferred.

Very particular preference is given to the aminobenzoylsulfamic acid amides of the formula IIA.1-a (≡II where Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IIA.1-a.1 to IIA.1-a.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the aminobenzoylsulfamic acid amides of the formula IIA.1-b (≡II where Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=H, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IIA.1-b.1 to IIA.1-b.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the aminobenzoylsulfamic acid amides of the formula IIA.1-c (≡II where Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IIA.1-c.1 to IIA.1-c.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the aminobenzoylsulfamic acid amides of the formula IIA.1-d (m II where Ar=Ar-1 where R^(a)=F and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²) where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IIA.1-d.1 to IIA.1-d.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the aminobenzoylsulfamic acid amides of the formula IIA.1-e (≡II where Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IIA.1-e.1 to IIA.1-e.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the aminobenzoylsulfamic acid amides of the formula IIA.1-f (≡II where Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds IIA.1-f.1 to IIA.1-f.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

The nitrobenzoylsulfamic acid amides of the formula V are likewise novel and also represent useful intermediates for preparing the iso(thio)cyanatobenzoylsulfamic acid amides I. They also form part of the subject-matter of the present invention.

Accordingly, the present invention also relates to the nitro compounds of the formula V, in particular to compounds of the formula VA (≡V where Ar=Ar-1),

where R^(a), R^(b), R^(c), R^(d) and A are as defined above. In the formula VA, R^(a), R^(b), R^(c), R^(d) and A preferably denote those radicals which have already been mentioned in connection with the description of the compound I according to the invention as being preferred for these variables.

Very particular preference is given to the compounds of the formula VA.1,

in which the variables R¹, R², R^(a), R^(b), R^(c), R^(d) are as defined above. In the formula VA.1, the variables R¹, R², R^(a), R^(b), R^(c), R^(d) preferably have those meanings which have already been mentioned in connection with the description of the compounds IA.1 according to the invention as being preferred.

Very particular preference is given to the nitrobenzoylsulfamic acid amides of the formula VA.1-a V where Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds VA.1-a.1 to VA.1-a.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the nitrobenzoylsulfamic acid amides of the formula VA.1-b (≡V where Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=H, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds VA.1-b.1 to VA.1-b.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the nitrobenzoylsulfamic acid amides of the formula VA.1-c (≡V where Ar=Ar-1 where R^(a)=Cl and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds VA.1-c.1 to VA.1-c.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the nitrobenzoylsulfamic acid amides of the formula VA.1-d (m V where Ar=Ar-1 where R^(a)=F and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds VA.1-d.1 to VA.1-d.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the nitrobenzoylsulfamic acid amides of the formula VA.1-e (≡V where Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=F, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds VA.1-e.1 to VA.1-e.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

Very particular preference is given to the nitrobenzoylsulfamic acid amides of the formula VA.1-f V where Ar=Ar-1 where R^(a)=CN and R^(b)=R^(d)=hydrogen and R^(c)=Cl, A=NR¹R²), where R¹, R² have the meanings mentioned above, and in particular the meanings mentioned as being preferred. Examples of such compounds are the compounds VA.1-f.1 to VA.1-f.495 in which the variables R¹, R² together have the meanings given in one row of Table 1.

The bifunctional phenyl iso(thio)cyanates I according to the invention can be used as starting materials for pharmacologically active compounds or crop protection agents. WO 01/83459, for example, describes herbicidal 3-(triazolidinedione)-substituted benzoic acid sulfamoyl amides of the formula below

where X¹ is hydrogen, halogen, C₁-C₄-alkyl, X² is hydrogen, CN, CS—NH₂, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, R¹¹ and R²¹ have the meanings given above for R¹ and R², respectively, and are in particular hydrogen, unsubstituted or substituted hydroxyl, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-alkynyl, C₃-C₇-cycloalkyl, phenyl, benzyl or C₅-C₇-cycloalkenyl, or R¹¹ and R²¹ together with the nitrogen atom to which they are attached form a 3- to 7-membered heterocyclic ring, and Q is a radical of the formula a

where W is as defined above, W′ is O or S and R³ and R⁴ independently of one another are one of the radicals below: hydrogen, cyano, amino, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₃-C₇-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₃-C₆-alkynyl, benzyl, OR⁵ (where R⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₇-cycloalkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, unsubstituted or substituted phenyl or unsubstituted or substituted benzyl), C₁-C₃-cyanoalkyl, or R³ and R⁴ together with the nitrogen atoms to which they are attached form a four- to seven-membered heterocycle which is optionally interrupted by sulfur, oxygen, a group NR⁶ (where R⁶ is as defined above) or nitrogen and which is unsubstituted or mono- or polysubstituted by halogen or C₁-C₄-alkyl, and is in particular a radical of the formula b:

where W is as defined above and W′ and Z independently of one another are oxygen or sulfur.

The herbicides described in WO 01/83459 are not always obtainable in sufficient yields and purity. The processes described therein are based, for example:

-   A) on the condensation of a substituted benzoic acid with a     substituted sulfamic acid amide in the presence of     N,N-carbonyldiimidazole (CDI) or the conversion of the carboxylic     acid into its acid chloride and subsequent reaction of the acid     chloride with the sulfamic acid amide.

-   -   Here, the variables R¹¹, R²¹, X¹ and X² may have the meanings         mentioned above, and Q is a 5- or 6-membered heterocycle, for         example a radical a or b.     -   This process has the disadvantage that the benzoic acid used can         only be obtained from the ester precursor by cleavage with boron         tribromide, with the corresponding amount of salt being         produced. Moreover, the yield of the condensation with sulfamic         acid amides is only from 16 to 45%. Even the detour via an acid         chloride, prepared beforehand, gives the desired benzoylsulfamic         acid amide in a yield of only 26%, and in addition, its         impurities have to be removed chromatographically.

-   B) The substitution of a halogen radical by the heterocyclic radical     Q:

-   -   Here, the variables R¹¹, R²¹, X¹ and X² may have the meanings         mentioned above, Hal is fluorine, chlorine or bromine and Q is a         5- or 6-membered heterocycle, for example a radical a or b.     -   This process has the disadvantages that the halogenated aromatic         compound used has to be provided in a complicated manner via a         Sandmeyer reaction, and moreover an unsatisfactory selectivity         in the reaction of the 5-halo-substituted compound, compared to         the—activated—2,4-dihalosubstituents present in the same         molecule.

Accordingly, all of the prior-art processes for preparing 3-(triazolidinedione)-substituted benzoylsulfamoylamides and their sulfur analogs are unsatisfactory with respect to a short reaction time, a simple practice of the reaction, yields and purity of the end products, and are therefore uneconomical.

Accordingly, it is another object of the present invention to provide a process for preparing compounds of the formula VI,

where W, Ar and A are as defined in claim 1, W′ is O or S and R³ and R⁴ independently of one another are hydrogen, cyano, amino, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-haloalkoxy, C₃-C₇-cycloalkyl, C₂-C₆-alkenyl, C₂-C₆-haloalkenyl, C₃-C₆-alkynyl, benzyl, OR⁵ (where R⁵ is hydrogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₇-cycloalkyl, C₂-C₆-alkenyl, C₃-C₆-alkynyl, unsubstituted or substituted phenyl or unsubstituted or substituted benzyl), C₁-C₃-cyanoalkyl, or R³ and R⁴ together with the nitrogen atoms to which they are attached form a four- to seven-membered heterocycle which is optionally interrupted by sulfur, oxygen, a group NR⁶ (where R⁶ is as defined above) or nitrogen and which is unsubstituted or mono- or polysubstituted by halogen or C₁-C₄-alkyl.

Surprisingly, it has now been found that, starting with the compounds of the formula I according to the invention, in particular the compounds of the formula IA, it is possible to prepare the compounds of the formula VI described in WO 01/83459 in a much more simple manner, without side reactions and in higher yields and purity.

Accordingly, the present invention also provides a process for preparing compounds of the formula VI

where R³, R⁴, W, W′, Ar, A are as defined above which comprises the following steps

-   (i) reaction of a compound of the formula I as defined above with an     oxadiazinecarboxylic acid ester of the formula VII,

-   -   where W′ is as defined above and R′ is C₁-C₄-alkyl, giving a         urea derivative of the formula VIII

-   -   where the variables R³, R⁴, R′, W, W′, Ar and A are as defined         above, and

-   (ii) cyclization of the resulting intermediate VIII, giving a     compound of the formula VI.

Step (i) is carried out in a manner known per se, for example as described in WO 02/20531. In general, the iso(thio)cyanate of the formula I according to the invention is added to a compound of the formula VII, preferably in a solvent. Suitable solvents are hydrocarbons, such as pentane, hexane, cyclopentane, cyclohexane, toluene, xylene; chlorinated hydrocarbons, such as methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene, 1,2-, 1,3- or 1,4-dichlorobenzene; ethers, such as 1,4-dioxane, anisole; glycol ethers, such as dimethyl glycol ether, diethyl glycol ether, diethylene glycol dimethyl ether; esters, such as ethyl acetate, propyl acetate, methyl isobutyrate, isobutyl acetate; carboxamides, such as N,N-dimethylformamide, N-methylpyrrolidone; nitrated hydrocarbons, such as nitrobenzene, nitriles, such as acetonitrile, propionitrile, butyronitrile or isobutyronitrile; or else mixtures of individual solvents. The addition is generally carried out over a period of from 5 to 30 minutes. During the addition, the temperature is usually from 10 to 25° C. To bring the reaction to completion, the mixture is stirred for another 0.5 to 24 hours at from 20 to 80° C. It is, of course, also possible to initially charge the iso(thio)cyanate I in one of the abovementioned solvents, to add the compound VII and then to bring the reaction to completion as described above. Usually, from 0.9 to 1.4 mol, preferably from 0.95 to 1.1 mol and particularly preferably from 0.98 to 1.15 mol of the compound VII are employed per mole of the compound I. The compound of the formula VII used in step (i) is known or can be prepared similarly to the process described in WO 02/20531.

Step (ii) is again carried out in a manner known per se, for example as described in WO 02/20531, by treating the compound of the formula VIII with a base.

Suitable bases are, in principle, all compounds capable of abstracting the acidic proton of the NH group of the urea function in the compounds of the formula VIII. These include oxo bases, nitrogen bases and hydride bases.

The oxo bases include, for example, inorganic bases, such as alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal bicarbonates, and also alkali metal and alkaline earth metal carbonates, for example lithium hydroxide, bicarbonate or carbonate, sodium hydroxide, bicarbonate or carbonate, potassium hydroxide, bicarbonate or carbonate, calcium hydroxide, bicarbonate or carbonate, or magnesium hydroxide, bicarbonate or carbonate. Suitable oxo bases are likewise alkali metal alkoxides, in particular those of lithium, sodium or potassium, where, in general, alkoxides of C₁-C₆-, preferably C₁-C₄-alkanols, such as sodium methoxide, ethoxide, n-butoxide or tert-butoxide or potassium methoxide, ethoxide, n-butoxide or tert-butoxide are used. The nitrogen bases include primary, secondary or, preferably, tertiary amines, for example trialkylamines, such as triethylamine, tri-n-propylamine, N-ethyldiisopropylamine; cycloaliphatic amines, such as N,N-dimethylcyclohexylamine; cyclic amines, such as azabicyclo[2.2.2]octane (=triethylenediamine), N-methylpyrrolidine, N-ethylpiperidine; dialkylanilines, such as dimethylaminoaniline; p-dimethylaminopyridine; furthermore aromatic nitrogen heterocycles, such as pyridine, α-, β- or γ-picoline, 2,4- and 2,6-lutidine, quinoline, quinazoline, quinoxaline, pyrimidine; and also tertiary amides, for example dimethylformamide, N-methylformamide, N-methylpyrrolidone or tetramethylurea.

Suitable hydride bases are, for example, alkali metal hyrides, such as sodium hydride or potassium hydride. Preferred bases are tertiary amines, in particular trialkylamines.

Preference is given to using from 0.9 to 1.4 mol, in particular from 0.95 to 1.2 mol and with particular preference from 0.98 to 1.15 mol of the compound VIII per mole of base.

For the reaction of the compound VIII with the base, the compound VIII is preferably initially charged in one of the solvents mentioned above or in a solvent mixture, and the base is added with mixing, for example with stirring, to the reaction mixture. The addition of the base is preferably carried out at a temperature in the range from 0 to 50° C. and in particular from 10 to 30° C.

In general, the components are then allowed to react for another 10 minutes to 48 hours at from 20 to 150° C., preferably from 20 to 100° C. and in particular from 20 to 60° C., to bring the reaction to completion. In the case of thioureas of the formula VIII (W═S), the reaction is generally substantially complete (conversion>90%) after 0.5-10 hours, and in the case ureas of the formula VIII (W═O) after 4-48 hours and in particular after 8-24 hours. However, it is also possible to initially charge the base, preferably in one of the solvents mentioned above, followed by addition of the compound VIII and conclusion of the reaction as above.

The concentration of the starting materials in the solvent is generally in the range from 0.5 to 5 mol/l, preferably in the range from 0.2 to 2 mol/l.

Work-up of the reaction is carried out in a customary manner, for example by aqueous extraction, by dialysis and/or chromatographically.

The present process relates in particular to the preparation of compounds VIA

where R³ and R⁴ are as defined above and the variables W, W′, R^(a), R^(b), R^(c), R^(d), A have the meanings given above and in particular the meanings which have already been mentioned in connection with the description of compound IA as being preferred for these variables. In this case, the compound used in the process according to the invention for preparing the compound VIA is a compound of the formula IA, preferably a compound of the formula IA.1.

A preferred compound of the formula VII is, for example, a compound of the formula (VII′)

where Z is O or S and R′ is C₁-C₄-alkyl. This compound is known from WO 02/20531.

By this route, starting with the compounds of the formula IA, it is possible, in accordance with Scheme 3 below, to prepare in particular compounds of the formula IX (=compound VIA where R^(b)=R^(d)=H, A=NR¹R², W=W′=O and R³, R⁴ are CH₂CH₂OCH₂).

Here, the variables R^(a), R^(c), R¹ and R² have the meanings mentioned above.

The process according to the invention is, with respect to yields and purity, superior to the process described in WO 01/83459. Moreover, its practice is much easier. With respect to the disadvantages of the process known from WO 01/83459, reference is made to what has been said above.

The examples below serve to illustrate the invention

-   I Preparation of the nitrobenzoylsulfamic acid amides (intermediate     of the formula VA.1; intermediates VA.1-1 to VA.1-24):

EXAMPLE 1 N-(2-Chloro-4-fluoro-5-nitrobenzoyl)-N′-n-propyl-N′-allyl-sulfamide (VA.1-a.241)

At from −5° C. to 0° C., 11.62 g (0.0474 mol) of 2-chloro-4-fluoro-5-nitrobenzoyl chloride in 50 ml methylene chloride were added with stirring, over 30 minutes, to a mixture of 8.50 g (0.048 mol) of N′-propyl-N′-allylsulfamide, 10.38 g (0.103 mol) of triethylamine and 0.09 g (0.736 mmol) of 4-N,N-dimethylaminopyridine in 90 ml of methylene chloride. The funnel was rinsed with 10 ml of the solvent. The mixture was initially stirred at 0° C. for 1 hour and then at 22° C. for 2 hours. 50 ml of 1N hydrochloric acid were then added, the mixture was stirred and the phases were separated. The organic phase was washed two more times with 1N hydrochloric acid and the aqueous phase was extracted with methylene chloride. Drying of the organic phase over magnesium sulfate was followed by filtration and concentration of the solution. The residue was triturated with diethyl ether/pentane, filtered off with suction and dried, giving 18.41 g (91.9% of theory) of the title compound of melting point (m.p.) of 110-112° C.

The intermediates VA.1 (compounds of the formula VI where Ar=Ar-1 where R^(b), R^(d)=H and R¹ and R² have the meanings given in Table 1) of Examples 2 to 24 listed in Table 2 were obtained in an analogous manner.

TABLE 2 (VA.1)

m.p. [° C.]/ ¹H-NMR (400 MHz, Example/ CDCl₃) δ No. ¹⁾ R^(c) R^(a) R¹ R² (ppm) 1 F Cl n-C₃H₇ CH₂═CH—CH₂ 110-112 VA.1-a.241 2 F Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 137-138 VA.1-a.490 3 F Cl i-C₃H₇ HC≡C—CH₂ 160-161 VA.1-a.387 4 H Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 151-152 VA.1-b.492 5 H Cl n-C₃H₇ CH₂═CH—CH 132-134 VA.1-b.241 6 H Cl i-C₃H₇ HC≡C—CH₂ 138-140 VA.1-b.387 7 F Cl CH₃ i-C₃H₇ 121-122 VA.1-a.86 8 F Cl CH₃ CH₃ VA.1-a.76 9 F Cl CH₃ C₂H₅ VA.1-a.77 10 F Cl CH₃ n-C₃H₇ VA.1-a.84 11 F Cl CH₃ c-C₃H₅ VA.1-a.98 12 F Cl CH₃ n-C₄H₉ VA.1-a.85 13 F Cl CH₃ i-C₄H₉ VA.1-a.88 14 F Cl CH₃ sec-C₄H₉ VA.1-a.87 15 F Cl CH₃ tert-C₄H₉ VA.1-a.89 16 F Cl CH₃ CH₂═CH—CH₂ VA.1-a.93 17 F Cl CH₃ HC≡C—CH₂ VA.1-a.96 18 F Cl CH₃ C₆H₅ VA.1-a.107 19 F Cl CH₃ cyclohexyl VA.1-a.445 20 F Cl C₂H₅ C₆H₅ VA.1-a.181 21 F Cl C₂H₅ cyclohexyl VA.1-a.446 22 F Cl C₂H₅ i-C₃H₇ VA.1-a.160 23 F Cl C₂H₅ CH₂═CH—CH₂ VA.1-a.167 24 H Cl CH₃ sec.-C₄H₉ 8.4 (d, VA.1.-b.87 1H), 8.2 (m, 1H), 7.6 (d, 1H), 4.0 (sept., 1H), 2.9 (s, 3H), 1.5 (m, 2H), 1.2 (d, 6H), 0.9 (t, 3H). 1) compound number according to Table 1

-   II Preparation of the aminobenzoylsulfamic acid amides of the     formula IIA (intermediates IIA.1):     IIa Reduction of the Nitro Group Using Iron Powder In Acetic Acid

EXAMPLE 25 N-(5-Amino-2-chloro-4-fluorobenzoyl)-N′-allyl-N′-n-propylsulfamide (IIA.1-a.241)

With stirring, a solution of 17.1 g (45.02 mmol) of the compound VA.1-a.241 from Example 1 in a mixture of 5 ml of tetrahydrofuran and 40 ml of acetic acid was added at 70 to 75° C. over a period of 25 minutes to a suspension of 7.54 g (135.072 mmol) of iron powder in 60 ml of acetic acid. The mixture was stirred at 70 to 75° C. for another hour and then allowed to cool and concentrated under reduced pressure. The residue was stirred with ethyl acetate and filtered, and the precipitate was washed with ethyl acetate. The filtrate was stirred with activated carbon and magnesium sulfate, filtered, washed and concentrated. The residue was turned into a paste using ethyl acetate, triturated with pentane, filtered off with suction and dried, giving 12.1 g (75.3% of theory) of the title compound of melting point 104-106° C.

IIb Catalytic Hydrogenation of the Nitro Group

EXAMPLE 31 N-(5-Amino-2-chloro-4-fluorobenzoyl)-N′-methyl-N′-isopropylsulfamide (IIA.1-a.86)

112.0 g (0.317 mol) of the compound VA.1-a.86 from Example 7 and 100 g of Raney nickel in 1200 ml of methanol were initially charged in a hydrogenation apparatus. With stirring, the apparatus was flushed with 10 l of nitrogen and with 10 l of hydrogen. With stirring, the mixture was hydrogenated at 22-26° C. using a hydrogen pressure of 0.1 bar. In total, 21.3 l of hydrogen were taken up. The mixture was vented and again flushed with 10 l of nitrogen. The reaction mixture was filtered off with suction through silica gel and the filtrate was concentrated under reduced pressure. This gave 100.5 g (97% of theory) of the title compound of melting point 160-162° C. (purity according to HPLC: 99.1%).

Starting with the nitrobenzoylsulfamic acid amides VA.1 listed in Table 2, the intermediates IIA (compounds of the formula II where Ar=Ar-1 where R^(b), R^(d)=H and R¹ and R² have the meanings given in Table 1) of Example 26 to Example 48 listed in Table 3 were obtained in an analogous manner.

TABLE 3 IIA.1

m.p. [° C.]/ ¹H-NMR (400 MHz, Example/ CDCl₃) δ No. ¹⁾ R^(c) R^(a) R¹ R² (ppm) 25 F Cl n-C₃H₇ CH₂═CH—CH₂ 104-106 IIA.1-a.241 26 F Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 144-145 IIA.1-a.492 27 F Cl i-C₃H₇ HC≡C—CH₂ 153-154 IIA.1-a.387 28 H Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 139 IIA.1-b.492 29 H Cl n-C₃H₇ CH₂═CH—CH₂ 138 IIA.1-b.241 30 H Cl i-C₃H₇ HC≡C—CH₂ 139-140 IIA.1-b.387 31 F Cl CH₃ i-C₃H₇ 160-162 IIA.1-a.86 32 F Cl CH₃ CH₃ IIA.1-a.76 33 F Cl CH₃ C₂H₅ IIA.1-a.77 34 F Cl CH₃ n-C₃H₇ IIA.1-a.84 35 F Cl CH₃ c-C₃H₅ IIA.1-a.98 36 F Cl CH₃ n-C₄H₉ IIA.1-a.85 37 F Cl CH₃ i-C₄H₉ IIA.1-a.88 38 F Cl CH₃ sek.-C₄H₉ IIA.1-a.87 39 F Cl CH₃ tert.-C₄H₉ IIA.1-a.89 40 F Cl CH₃ CH₂═CH—CH₂ IIA.1-a.93 41 F Cl CH₃ HC≡C—CH₂ IIA.1-a.96 42 F Cl CH₃ C₆H₅ IIA.1-a.107 43 F Cl CH₃ Cyclohexyl IIA.1-a.445 44 F Cl C₂H₅ C₆H₅ IIA.1-a.181 45 F Cl C₂H₅ Cyclohexyl IIA.1-a.446 46 F Cl C₂H₅ i-C₃H₇ IIA.1-a.160 47 F Cl C₂H₅ CH₂═CH—CH₂ IIA.1-a.167 48 H Cl CH₃ sek.-C₄H₉ 8.8 (br. IIA.1-b.87 s), 7.2 (d, 1H), 7.1 (m, 1H), 6.8 (d, 1H), 4.0 (m, 1H), 3.8 (br. s, 2H), 2.9 (s, 3H), 1.6-1.4 (m, 2H), 1.2 (d, 3H), 0.9 (t, 3H) 1) compound number according to Table 1 III Preparation of the phenyl iso(thio)cyanates I

EXAMPLE 109 N-(2-Chloro-4-fluoro-5-isocyanatobenzoyl)-N′-allyl-N′-n-propyl-sulfamide (IA.1-a.241)

With stirring at 15 to 25° C., 4.7 ml of a 4 M solution of HCl in dioxane (corresponds to 18.9 mmol of hydrogen chloride) was added to 6.0 g (17.2 mmol) of the compound IIA.1-a.241 from Example 25 in 50 ml of dioxane. The mixture was stirred at 22° C. for another hour. With stirring and slowly increasing the temperature to 95° C., 3.4 g (34.3 mmol) of phosgene were introduced over a period of 1 h. Unreacted phosgene was flushed out with nitrogen. The reaction mixture was then concentrated under reduced pressure, the residue was triturated with pentane and the supernatant was decanted off and concentrated under reduced pressure. This gave 6.5 g (95.8% of theory, purity according to ¹H-NMR: 95%) of the title compound of melting point 85-95° C. (decomp.). IR (KBr): N═C═O 2265 cm⁻¹; C═O 1724 cm⁻¹.

EXAMPLE 94 N-(2-Chloro-4-fluoro-5-isocyanatobenzoyl)-N′-methyl-N′-isopropyl-sulfamide (IA.1-a.86)

A) by reaction with phosgene

At 22° C. and with stirring, phosgene was introduced into a solution of 5.0 g (15.4 mmol) of the compound IIA.1-a.86 from Example 31 in 50 ml of dioxane. Over a period of 20 minutes, the temperature was increased to the reflux temperature of the solvent mixture. Phosgene was introduced for another hour and the mixture was then allowed to cool to room temperature and flushed with nitrogen. The reaction mixture was then concentrated under reduced pressure, initially at 22° C. and then at 70° C. The residue was triturated with n-hexane, the n-hexane was decanted and the residue was dried at 70° C., giving 5.5 g (99.8% of theory of a ¹H-NMR purity of 98%) of the title compound of melting point 146-149° C.

B) by reaction with diphosgene

With stirring at 10° C., 6.11 g (30.9 mmol) of diphosgene were added dropwise to a solution of 5.0 g (15.4 mmol) of the compound IIA.1-a.86 in 50 ml of dioxane. The reaction mixture was allowed to warm to 22° C., and stirring was continued for a further 1.5 hours. According to thin-layer chromatography, the reaction was then complete. The mixture was stirred overnight and then flushed with nitrogen and worked-up as described above in Example 94A. This gave 5.5 g (99.8% of theory of a ¹H-NMR purity of 98%) of the title compound of melting point 148-150° C.

EXAMPLE 118 N-(2-Chloro-4-fluoro-5-isocyanatobenzoyl)-N-(4-methylpiperidine-sulfonamide) (IA.1-a.492)

With stirring at 20 to 25° C., 2.6 ml of a 4 M HCl solution (corresponds to 0.38 g (10.3 mmol) of hydrogen chloride) in dioxane were added to 1.8 g (5.1 mmol) of the compound IIA.1-a.492 from Example 26 in 50 ml of dioxane. The mixture was stirred at 22° C. for another hour. A further 1.12 g (5.66 mmol) of diphosgene were then added with stirring, and the mixture was stirred at 22° C. for 30 min., heated slowly to 95° C. and stirred for another hour. After cooling to room temperature, the mixture was concentrated under reduced pressure, the residue was triturated with pentane, the supernatant solution was decanted and the solution was reconcentrated under reduced pressure. This gave 2.0 g (98.3% of theory, of a ¹H-NMR purity 95%) of the title compound of melting point 122-124° C. (decomp.), 135° C. clear. IR (KBr): N═C═O 2246 cm⁻¹; C═O 1697 cm⁻¹.

EXAMPLE 193 N-(2-Chloro-4-fluoro-5-isothiocyanatobenzoyl)-N′-allyl-N′-n-propyl-sulfamide (IA.1-g.241)

With stirring at 22° C., 1.1 g (9.4 mmol) of thiophosgene were added to 3.0 g (8.6 mmol) of the compound IIA.1-a.241 from Example 25 in 50 ml of ethyl acetate, and the mixture was then stirred for another hour and then heated at 75° C. and stirred for another hour. After concentration under reduced pressure, the residue was triturated with pentane, filtered off with suction and dried, giving 3.4 g (96.1% of theory, purity according to ¹H-NMR 95%) of the title compound of melting point 83-85° C.

IR (KBr): N═C═S 2030 cm⁻¹, C═O 1725 curl.

Starting with the aminobenzoylsulfamic acid amides IA.1 listed in Table 3, the title compounds IA.1 (compounds of the formula I where Ar=Ar-1 where R^(b), R^(d)═H and R¹ and R² have the meanings given in Table 1) of Example 49 to Example 216 listed in Table 4 were obtained in an analogous manner.

TABLE 4 (IA.1)

Ex. W R^(c) R^(a) R¹ R² m.p. [° C.] 49 O H Cl CH₃ CH₃ 50 O H Cl CH₃ C₂H₅ 51 O H Cl CH₃ n-C₃H₇ 52 O H Cl CH₃ i-C₃H₇ 53 O H Cl CH₃ c-C₃H₅ 54 O H Cl CH₃ n-C₄H₉ 55 O H Cl CH₃ i-C₄H₉ 56 O H Cl CH₃ sec.-C₄H₉ 57 O H Cl CH₃ tert.-C₄H₉ 58 O H Cl C₂H₅ C₂H₅ 59 O H Cl C₂H₅ n-C₃H₇ 60 O H Cl C₂H₅ i-C₃H₇ 61 O H Cl C₂H₅ c-C₃H₅ 62 O H Cl C₂H₅ n-C₄H₉ 63 O H Cl C₂H₅ i-C₄H₉ 64 O H Cl C₂H₅ sec.-C₄H₉ 65 O H Cl CH₂═CH—CH₂ CH₃ 66 O H Cl CH₂═CH—CH₂ C₂H₅ 67 O H Cl CH₂═CH—CH₂ n-C₃H₇ 102-104 (Zers.) 68 O H Cl CH₂═CH—CH₂ i-C₃H₇ 69 O H Cl CH₂═CH—CH₂ n-C₄H₉ 70 O H Cl CH₂═CH—CH₂ sec.-C₄H₉ 71 O H Cl HC≡C—CH₂ CH₃ 72 O H Cl HC≡C—CH₂ C₂H₅ 73 O H Cl HC≡C—CH₂ n-C₃H₇ 74 O H Cl HC≡C—CH₂ i-C₃H₇ 133-141 (Zers.) 75 O H Cl HC≡C—CH₂ n-C₄H₉ 76 O H Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 110-115 (Zers.) 77 O H Cl CH₃ cyclohexyl 78 O H Cl CH₃ C₆H₅ 79 O H Cl C₂H₅ cyclohexyl 80 O H Cl C₂H₅ C₆H₅ 81 O H Cl [CH₂]₄ 82 O H Cl [CH₂]₅ 83 O H CN CH₃ CH₃ 84 O H CN CH₃ C₂H₅ 85 O H CN CH₃ i-C₃H₇ 86 O H CN CH₃ n-C₃H₇ 87 O H CN CH₃ i-C₄H₉ 88 O H CN CH₃ sec.-C₄H₉ 89 O H CN CH₃ cyclohexyl 90 O H CN CH₃ C₆H₅ 91 O F Cl CH₃ CH₃ 92 O F Cl CH₃ C₂H₅ 93 O F Cl CH₃ n-C₃H₇ 94 O F Cl CH₃ i-C₃H₇ 144-148 95 O F Cl CH₃ c-C₃H₅ 96 O F Cl CH₃ n-C₄H₉ 97 O F Cl CH₃ i-C₄H₉ 98 O F Cl CH₃ sec.-C₄H₉ 99 O F Cl CH₃ tert.-C₄H₉ 100 O F Cl C₂H₅ C₂H₅ 101 O F Cl C₂H₅ n-C₃H₇ 102 O F Cl C₂H₅ i-C₃H₇ 103 O F Cl C₂H₅ c-C₃H₅ 104 O F Cl C₂H₅ n-C₄H₉ 105 O F Cl C₂H₅ i-C₄H₉ 106 O F Cl C₂H₅ sec.-C₄H₉ 107 O F Cl CH₂═CH—CH₂ CH₃ 108 O F Cl CH₂═CH—CH₂ C₂H₅ 109 O F Cl CH₂═CH—CH₂ n-C₃H₇ 85-95 (Zers.) 110 O F Cl CH₂═CH—CH₂ i-C₃H₇ 111 O F Cl CH₂═CH—CH₂ n-C₄H₉ 112 O F Cl CH₂═CH—CH₂ sec.-C₄H₉ 113 O F Cl HC≡C—CH₂ CH₃ 114 O F Cl HC≡C—CH₂ C₂H₅ 115 O F Cl HC≡C—CH₂ n-C₃H₇ 116 O F Cl HC≡C—CH₂ i-C₃H₇ 124-126 (Zers.) 117 O F Cl HC≡C—CH₂ n-C₄H₉ 118 O F Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 122-124 (Zers.) 119 O F Cl CH₃ cyclohexyl 120 O F Cl CH₃ C₆H₅ 121 O F Cl C₂H₅ cyclohexyl 122 O F Cl C₂H₅ C₆H₅ 123 O F Cl [CH₂]₄ 124 O F Cl [CH₂]₅ 125 O F CN CH₃ CH₃ 126 O F CN CH₃ C₂H₅ 127 O F CN CH₃ i-C₃H₇ 128 O F CN CH₃ n-C₃H₇ 129 O F CN CH₃ i-C₄H₉ 130 O F CN CH₃ sec.-C₄H₉ 131 O F CN CH₃ cyclohexyl 132 O F CN CH₃ C₆H₅ 133 S H Cl CH₃ CH₃ 134 S H Cl CH₃ C₂H₅ 135 S H Cl CH₃ n-C₃H₇ 136 S H Cl CH₃ i-C₃H₇ 137 S H Cl CH₃ c-C₃H₅ 138 S H Cl CH₃ n-C₄H₉ 139 S H Cl CH₃ i-C₄H₉ 140 S H Cl CH₃ sec.-C₄H₉ 141 S H Cl CH₃ tert.-C₄H₉ 142 S H Cl C₂H₅ C₂H₅ 143 S H Cl C₂H₅ n-C₃H₇ 144 S H Cl C₂H₅ i-C₃H₇ 145 S H Cl C₂H₅ c-C₃H₅ 146 S H Cl C₂H₅ n-C₄H₉ 147 S H Cl C₂H₅ i-C₄H₉ 148 S H Cl C₂H₅ sec.-C₄H₉ 149 S H Cl CH₂═CH—CH₂ CH₃ 150 S H Cl CH₂═CH—CH₂ C₂H₅ 151 S H Cl CH₂═CH—CH₂ n-C₃H₇ 99-100 152 S H Cl CH₂═CH—CH₂ i-C₃H₇ 153 S H Cl CH₂═CH—CH₂ n-C₄H₉ 154 S H Cl CH₂═CH—CH₂ sec.-C₄H₉ 155 S H Cl HC≡C—CH₂ CH₃ 156 S H Cl HC≡C—CH₂ C₂H₅ 157 S H Cl HC≡C—CH₂ n-C₃H₇ 158 S H Cl HC≡C—CH₂ i-C₃H₇ 163-164 159 S H Cl HC≡C—CH₂ n-C₄H₉ 160 S H Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 143-144 161 S H Cl CH₃ cyclohexyl 162 S H Cl CH₃ C₆H₅ 163 S H Cl C₂H₅ cyclohexyl 164 S H Cl C₂H₅ C₆H₅ 165 S H Cl [CH₂]₄ 166 S H Cl [CH₂]₅ 167 S H CN CH₃ CH₃ 168 S H CN CH₃ C₂H₅ 169 S H CN CH₃ i-C₃H₇ 170 S H CN CH₃ n-C₃H₇ 171 S H CN CH₃ i-C₄H₉ 172 S H CN CH₃ sec.-C₄H₉ 173 S H CN CH₃ cyclohexyl 174 S H CN CH₃ C₆H₅ 175 S F Cl CH₃ CH₃ 176 S F Cl CH₃ C₂H₅ 177 S F Cl CH₃ n-C₃H₇ 178 S F Cl CH₃ i-C₃H₇ 179 S F Cl CH₃ c-C₃H₅ 180 S F Cl CH₃ n-C₄H₉ 181 S F Cl CH₃ i-C₄H₉ 182 S F Cl CH₃ sec.-C₄H₉ 183 S F Cl CH₃ tert.-C₄H₉ 184 S F Cl C₂H₅ C₂H₅ 185 S F Cl C₂H₅ n-C₃H₇ 186 S F Cl C₂H₅ i-C₃H₇ 187 S F Cl C₂H₅ c-C₃H₅ 188 S F Cl C₂H₅ n-C₄H₉ 189 S F Cl C₂H₅ i-C₄H₉ 190 S F Cl C₂H₅ sec.-C₄H₉ 191 S F Cl CH₂═CH—CH₂ CH₃ 192 S F Cl CH₂═CH—CH₂ C₂H₅ 193 S F Cl CH₂═CH—CH₂ n-C₃H₇ 83-85 194 S F Cl CH₂═CH—CH₂ i-C₃H₇ 195 S F Cl CH₂═CH—CH₂ n-C₄H₉ 196 S F Cl CH₂═CH—CH₂ sec.-C₄H₉ 197 S F Cl HC≡C—CH₂ CH₃ 198 S F Cl HC≡C—CH₂ C₂H₅ 199 S F Cl HC≡C—CH₂ n-C₃H₇ 200 S F Cl HC≡C—CH₂ i-C₃H₇ 155-156 201 S F Cl HC≡C—CH₂ n-C₄H₉ 202 S F Cl CH₂—CH₂—CH(CH₃)—CH₂—CH₂ 152-153 203 S F Cl CH₃ cyclohexyl 204 S F Cl CH₃ C₆H₅ 205 S F Cl C₂H₅ cyclohexyl 206 S F Cl C₂H₅ C₆H₅ 207 S F Cl [CH₂]₄ 208 S F Cl [CH₂]₅ 209 S F CN CH₃ CH₃ 210 S F CN CH₃ C₂H₅ 211 S F CN CH₃ i-C₃H₇ 212 S F CN CH₃ n-C₃H₇ 213 S F CN CH₃ i-C₄H₉ 214 S F CN CH₃ sec.-C₄H₉ 215 S F CN CH₃ cyclohexyl 216 S F CN CH₃ C₆H₅

EXAMPLE 217 8-(5′-N-Isopropyl-N-methylsulfamoyl-carboxamido-4′-chloro-2′-fluorophenyl)-4-oxo-7,9-dioxo-1,2,8-triaza[4.3.0]nonane (Example 146 of WO 01/83459) 217.1: Methyl tetrahydro-N-(4-chloro-2-fluoro-5-N-isopropyl-N-methylsulfamoylcarboxamidophenyl)-4H-1,3,4-oxadiazine-3-carboxamide-4-carboxylate

Over a period of 5 minutes, 9.8 g (10.1 mmol) of methyl tetrahydro-4H-1,3,4-oxadiazine-4-carboxylate, as a 15% strength solution in 1,2-dichloroethane, were added at 22° C. and with stirring to a mixture of 3.5 g (10.1 mmol) of N-(2-chloro-4-fluoro-5-isocyanatobenzoyl)-N′-isopropyl-N′-methylsulfamide IA-a.86 from Example 94 in 100 ml of 1,2-dichloroethane, and the mixture was stirred for 18 hours. The reaction mixture was then purified by flash chromatography on silica gel using 200 ml portions of a mixture of methylene chloride/diethyl ether=1:6 as mobile phase. The solvent was removed under reduced pressure, giving 4.3 g (82.3% of theory) of methyl tetrahydro-N-(4-chloro-2-fluoro-5-N-isopropyl-N-methylsulfamoylcarboxamidophenyl)-4H-1,3,4-oxadiazine-3-carboxamide-4-carboxylate of melting point 69° C. (decomposition).

217.2: 8-(5′-N-Isopropyl-N-methylsulfamoylcarboxamido-4′-chloro-2′-fluorophenyl)-4-oxo-7,9-dioxo-1,2,8-triaza[4.3.0]nonane

In a reaction vessel fitted with stirrer and water separator, 0.85 g (1.7 mmol) of the compound from Example 217.1 was initially charged in 80 ml of toluene. With stirring, 0.18 g (1.8 mmol) of 97% pure sodium tert-butoxide was added at 22° C., and the mixture was then heated to reflux with stirring. The toluene was occasionally replaced. In total, the mixture was heated at reflux for 7 hours until the reaction mixture became more highly liquid and the solids were almost completely dissolved. After cooling, the reaction mixture was acidified using a 1M solution of HCl in 10 ml of diethyl ether and concentrated under reduced pressure. The residue was dissolved in methylene chloride, extracted with 1N hydrochloric acid and water, dried and concentrated under reduced pressure. This gave 0.67 g (76% of theory) of the title compound of melting point 112-118° C. Following trituration with diethyl ether, the melting point was 115-120° C. 

The invention claimed is:
 1. A phenyl iso(thio)cyanate of formula I,

where: W is oxygen or sulfur, Ar is phenyl which may be mono- or polysubstituted by the following groups: hydrogen, halogen, C₁-C₄-haloalkyl or cyano, and A is a radical derived from a primary or secondary amine or is NH₂,
 2. A phenyl iso(thio)cyanate of formula Ia,

wherein: W is oxygen or sulfur, A is a radical derived from a primary or secondary amine or is NH₂, and R^(a) is fluorine, chlorine or cyano, R^(c) is hydrogen, fluorine or chlorine and R^(b) and R^(d) are each hydrogen.
 3. A phenyl iso(thio)cyanate of the formula Ia as defined in claim 2, wherein A is a radical of the formula NR¹R² where R¹ and R² independently of one another represent hydrogen, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl or C₂-C₁₀-alkynyl which may be unsubstituted or substituted by one of the following radicals: C₁-C₄-alkoxy, C₁-C₄-alkylthio, CN, NO₂, formyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylaminocarbonyl, C₁-C₄-dialkylaminocarbonyl, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl, C₃-C₁₀-cycloalkyl, 3- to 8-membered heterocyclyl having one, two or three heteroatoms selected from the group consisting of O, S, N and a group NR⁶ (where R⁶ is hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl), phenyl, which may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-fluoroalkyl, C₁-C₄-alkyloxycarbonyl, trifluoromethylsulfonyl, C₁-C₃-alkylamino, C₁-C₃-dialkylamino, formyl, nitro and cyano, C₁-C₁₀-haloalkyl, C₂-C₁₀-haloalkenyl, C₂-C₁₀-haloalkynyl, C₃-C₈-cycloalkyl, C₃-C₁₀-cycloalkenyl, 3- to 8-membered heterocyclyl having one to three heteroatoms selected from the group consisting of O, S, N and a group NR⁶, wherein R⁶ is hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl), phenyl or naphthyl, where C₃-C₈-cycloalkyl, C₃-C₁₀-cycloalkenyl, 3- to 8-membered heterocyclyl, phenyl and naphthyl may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-fluoroalkyl, C₁-C₄-alkyloxycarbonyl, trifluoromethylsulfonyl, formyl, C₁-C₃-alkylamino, C₁-C₃-dialkylamino, phenoxy, nitro and cyano, or R¹ and R² together with the nitrogen atom to which they are attached form a saturated or partially unsaturated 5- to 8-membered nitrogen heterocycle which may be substituted by C_(1i)-C₄-alkyl, C₁-C₄-alkoxy and/or C₁-C₄-haloalkyl and may have one or two carbonyl groups, thiocarbonyl groups and/or one or two further heteroatoms selected from the group consisting of O, S, N and a group NR⁶, wherein R⁶ is as defined above, as ring members.
 4. A phenyl iso(thio)cyanate of formula Ia in claim 3, wherein R¹ and R² independently of one another are hydrogen, C₁-C₆-alkyl which is optionally substituted by a substituent selected from the group consisting of halogen, cyano, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, C₁-C₄-alkylthio, C₃-C₈-cycloalkyl, furyl, thienyl, 1,3-dioxolanyl, phenyl which for its part is optionally substituted by halogen or C₁-C₄-alkoxy, C₂-C₆-alkenyl, C₂-C₆- alkynyl, C₃-C₈-cycloalkyl or phenyl which is optionally substituted by 1 or 2 substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-fluoroalkyl, C₁-C₄-alkoxy, C₁-C₄-alkoxycarbonyl, nitro and C₁-C₃-dialkylamino, naphthyl or pyridyl or R¹ and R² together with the nitrogen atom to which they are attached form a five-, six-or seven-membered saturated or unsaturated nitrogen heterocycle which may optionally contain a further heteroatom selected from the group consisting of N, a group NR⁶ (where R⁶ is as defined above) and O as ring member and/or which may be substituted by one, two or three substituents selected from the group consisting of C₁-C₄-alkyl and C₄-C₄-haloalkyl.
 5. A process for preparing the phenyl iso(thio)cyanate of claim 1 which comprises reacting a compound of formula II,

where the variables Ar and A are as defined above or its HCl adduct, with phosgene, thiophosgene or diphosgene.
 6. The process of claim 5, wherein the HCl adduct of the compound of formula II is used.
 7. The process of claim 5, wherein from 0.9 to 2 molar equivalents of phosgene, thiophosgene or diphosgene are used, based on the moles of the compound of formula II.
 8. The process of claim 5, wherein the reaction of the HCl adduct of the compound of formula II is carried out in the presence of activated carbon.
 9. A process for preparing the phenyl iso(thio)cyanate of claim 2, wherein a compound of the formula IIa

wherein: R^(a), R^(b), R^(c) and R^(d) independently of one another are hydrogen, halogen, C₁-C₄-haloalkyl or cyano, and A is a radical derived from a primary or secondary amine or is NH₂ or its HCl adduct is reacted with phosgene, thiophosgene or diphosgene, giving a compound of the formula Ia

where the variables R^(a), R^(b), R^(c), R^(d), A are as defined above and W is oxygen or sulfur.
 10. The process of claim 5, wherein the radical A in formula I is NR¹R², where: R¹ and R² independently of one another represent hydrogen, C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl or C₂-C₁₀-alkynyl which may be unsubstituted or substituted by one of the following radicals: C₁-C₄-alkoxy, C₁-C₄-alkylthio, CN, NO₂, formyl, C₁-C₄-alkylcarbonyl, C₁-C₄-alkoxycarbonyl C₁-C₄-alkylaminocarbonyl, C₁-C₄-dialkylaminocarbonyl, C₁-C₄-alkylsulfinyl C₁-C₄-alkylsulfonyl, C₃-C₁₀-cycloalkyl, 3- to 8-membered heterocyclyl having one, two or three heteroatoms selected from the group consisting of O, S, N and a group NR⁶(where R⁶ is hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl), phenyl, which may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C_(4-alkoxy, C) ₁-C₄-fluoroalkyl, C₁-C₄-alkyloxycarbonyl, trifluoromethylsulfonyl, C₁-C₃-alkylamino, C₁-C₃-dialkylamino, formyl, nitro and cyano,C₀-C₁₀-haloalkyl, C₂-C₁₀-haloalkenyl, C₂-C₁₀-haloalkynyl, C₃-C₈-cycloalkyl, C₃-C₁₀-cycloalkenyl, 3- to 8-membered heterocyclyl having one to three heteroatoms selected from the group consisting of O, S, N and a group NR⁶ (where R⁶ is hydrogen, C₁-C₆-alkyl, C₃-C₆-alkenyl or C₃-C₆-alkynyl), phenyl or naphthyl, wherein the C₃-C₈-cycloalkyl, C₃-C₁₀-cycloalkenyl, 3- to 8-membered heterocyclyl, phenyl and naphthyl may have 1, 2, 3 or 4 substituents selected from the group consisting of halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-fluoroalkyl, C₁-C₄-alkyloxycarbonyl, trifluoromethylsulfonyl, formyl, C₁-C₃-alkylamino, C₁-C₃-dialkylamino, phenoxy, nitro and cyano, or R¹ and R² together with the nitrogen atom to which they are attached form a saturated or partially unsaturated 5- to 8-membered nitrogen heterocycle which may be substituted by C₁-C₄-alkyl, C₁-C₄-alkoxy and/or C₁-C₄-haloalkyl and may have one or two carbonyl groups, thiocarbonyl groups and/or one or two further heteroatoms selected from the group consisting of O, S, N and a group NR⁶,wherein R⁶ is as defined above, as ring members.
 11. The process of claim 5, wherein the compound of formula II is prepared by the following steps: i) reacting an aroyl compound of the formula III

in which the variable Ar is as defined above and X is halogen, OH or C₁-C₄-alkoxy with a sulfamic acid amide of the formula IV,

where A is as defined above and ii) reducing N-aroylsulfamic acid amide, obtained in step (i), of the formula V

where Ar and A are as defined above, giving a compound of the formula II.
 12. The process of claim 11, wherein in step (ii) the reduction is carried out in the presence of catalytic amounts of transition metals or transition metal compounds.
 13. The process of claim 11, wherein in step (ii) the reduction is carried out in the presence of iron and at least one C₁-C₄-carboxylic acid.
 14. A process of claim 11, wherein in step (ii) the reduction is carried out in the presence of Raney nickel and hydrogen. 